Facile synthesis of TiO2@ZIF-8/PANI composite: An

effective photocatalyst for toxic dye degradation

A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science

(M.S.) in Applied Chemistry and Chemical Engineering, University of Dhaka.

Submitted by
Examination Roll: 132406
Registration No: 2016-614-479
Session: 2020-21

Department of Applied Chemistry and Chemical Engineering

University of Dhaka
 DECLARATION CERTIFICATE

This is to certify that Examination Roll No. 132406, Reg. No. 2016-614-479, M.S session-2020-

21, Department of Applied Chemistry and Chemical Engineering, University of Dhaka, Dhaka,

Bangladesh, has carried out his M.S thesis on "Facile synthesis of TiO2@ZIF-8/PANI composite:

An effective photocatalyst for toxic dye degradation” under m supervision. He has successfully

completed his research work and ready to present his dissertation, which is required for the partial

fulfillment of his M.S degree. The candidate did the work submitted here and no part of this thesis

has been submitted elsewhere for any degree or diploma. The thesis contains no materials

previously published or written by any other person except reference is made in the text of the

thesis.

We have gone through the final draft of the thesis and recommend its submission for the degree of

Master of Science in Applied Chemistry and Chemical Engineering.

Supervisor

Dr. Mithun Sarker

Associate Professor
Department of Applied Chemistry and Chemical Engineering
Faculty of Engineering and Technology
University of Dhaka
 ACKNOWLEDGEMENT

First of all, I express my sincere gratitude to the almighty and omnipresent Allah for His mercy in
the successful completion of this thesis work.

My special thanks goes to my supervisor, Dr. Mithun Sarker, Associate Professor, Department of
Applied Chemistry and Chemical Engineering, University of Dhaka. His constant supervision and
spiritual encouragements throughout the entire period of my research work were instrumental in
putting together this dissertation. His commitment to supervision appeared to me encouraging
enough to move the research to the desired goal. Special thanks also go to him for providing all
kinds of departmental facilities for my research work.

I am really indebted to my co-supervisor, Dr. Md. Ashaduzzaman, Professor, Department of

Applied Chemistry and Chemical Engineering, University of Dhaka. His continuous support,
encouragement, helpful suggestions and supervision inspired me to complete my thesis work and
to write up my thesis successfully.

Again, I am grateful to my MS course coordinator Professor Dr. Shah Md. Masum and also the
Chairman, Professor Dr. Mohammad Nurnabi, Department of Applied Chemistry and Chemical
Engineering, University of Dhaka, for providing all necessary laboratory facilities for the smooth
completion of this dissertation. I am obliged to all teachers of the Department of Applied
Chemistry and Chemical Engineering, University of Dhaka. I would like to extend my thanks to
all members of this department for their cordial support.

I would also like to express my heartwarming thanks to the head, scientist and research fellow of
the Center for Advanced Research in Sciences (CARS), the University of Dhaka for helping me a
lot in doing my thesis works. I’m heartedly grateful for the NST fellowship provided by the
Ministry of Science and Technology, Government of Bangladesh.

I am especially grateful to my parents and family members for their love, inspiration, support and
encouragement during the course of this epic journey.

The Author

17 September, 2023
 Abstract

Metal-organic framework (MOF), an advanced class of materials, has drawn research interest due
to enormous surface area, tuneable pore size, high crystallinity, enhanced surface properties and
other unique properties. It is a kind of porous organic/inorganic hybrid material and also known
as porous coordination polymers. It consists of inorganic secondary building units of metal ions or
oxo-clusters and bridging organic linkers. Owing to its special properties, MOF is greatly suitable
for gas separation & stogare, electrochemical & biochemical sensors, catalysis of complex organic
reactions, vitamin & drug carrier, adsorption and photocatalytic removal of pollutants, and so on.
This research work is aimed to bring deep insights for utilizing this special type of material in the
perspective of Bangladesh. Here, in our country environmental pollution is one of the major
troubles to be countered in a right way. Especially, our aqueous environment is badly polluted by
organic as well as inorganic pollutants; textile dyes, heavy metals, pharmaceutical wastes and
others. Therefore, to minimize water pollution, a unique MOF material, denoted by TiO2@ZIF-
8/PANI 3D nanocomposite was successfully synthesized and characterized, as well as its eligibility
towards pollutants capture was investigated. For this purpose, pristine zeolitic imidazolate
framework 8 (ZIF8) was prepared from zinc nitrate hexahydrate, 2-methyl imidazole and methanol
(solvent) via reported procedure. Then post synthetic modifications were carried out for controlled
interfacial polymerization and TiO2 nanoparticle incorporation to create the final composite. The
synthesized nanocomposite was characterized by XRD, FTIR, XPS, FESEM, UV-DRS, PL, DLS,
Zeta potential and BET surface area analysis. Structural integrity was confirmed by detecting X-
ray diffraction. The XPS results reveal that TiO2 was successfully doped into the ZIF-8 (Zn-O
metal coordination bond). Interestingly, the nanocomposite exhibited BET surface area of 328.724
m²/g and band gap energy of 3.13 eV, proving it to be a good adsorbent and photocatalyst. This
assumption was found to be correct and it could effectively remove both cationic and anionic dyes
from aqueous solutions. From experimental data the maximum quantity of Auramine O (cationic
dye) removed was 187.5 mg/g with removal efficiency 93.40% in one hour. On the other hand, for
Remazol Red (anionic dye), these values were found to be 198.5 mg/g and 99.24% respectively
for the same time period. Primarily the outcome seemed to be very promising and future outlook
is needed for bringing this research to next level. However, a detailed analysis is provided in this
book.
 Chapter 1. Introduction

1.1. Background

Bangladesh's successful textile and apparel industries are well-known throughout the world. In
Bangladesh's fast rising economy, the textile industries are the most important source of economic
growth. The main source of foreign exchange profits is textile and garment exports. Bangladesh's
readymade garment (RMG) industry began operations in the late 1970s and quickly established
itself as a major economic actor in terms of export profits, job creation, poverty reduction, and
women's empowerment. As a fabric processing and finishing ingredient, organic dyestuffs are
widely used in the textile industry. These non-bio degradable organic dyestuffs from textile
industries are present in moderate concentrations in the range of 10-200 ppm in waste water which
find their ultimate way in the water bodies which may cause serious health hazards like cancer,
kidney failure etc. [1]. These organic dyes are also detrimental to the environment. These non-
biodegradable organic dyestuffs from the textile industry are found in moderate concentrations in
waste water, ranging from 10-200 ppm, and eventually end up in water bodies, posing major health
risks such as cancer, kidney failure, and other illnesses [1]. Environmentally, these organic colors
are also harmful. These colorful chemicals are unsightly and have a negative impact on the aquatic
ecosystem by blocking sunlight from entering the stream and limiting photosynthetic responses.
Vinyl sulfone dyes, commonly referred to as azo dyes, are a type of reactive dye that can be used
on cotton, silk, and wool. More than 30% of the utilized dyes are reported to stay in the spent dye
bath after the dyeing procedure in the literature. It is vital to remove these azo dyes from waste
water since they are carcinogenic and mutagenic [2, 3]. Bangladesh is now concerned about its
environmental problems. She has implemented policies related to "green technology," "eco-
friendly industry," "green banking," and so on. Thus, polluted waste water from textile mills would
be extremely toxic to humans and would serve as a warning sign. The correct treatment of waste
water that has been exposed to a water body is a difficulty for environmental scientists these days.
Various toxic metals, dangerous gases, organic and inorganic chemicals, dye substances, and other
pollutants can be found in industrial effluents [4,5]. During the dyeing process, around 10-15% of
dyes are discharged into the environment; hence, textile industry wastewater contains a large
amount of dyes [6]. The discharge of these untreated hazardous effluents has harmed natural flora
and animals, as well as posing a health danger to humans. Long-term exposure also causes deadly
diseases in people, such as cancer, delayed nerve responses, mutagenic alterations, neurological
problems, and so on [4,5]. Many dyes contain recognized carcinogens, such as benzidine, and are
known to accumulate in living organisms, providing a serious threat [7]. Today, the use of nitro
aromatic combinations and toxic colors in wastewater necessitates a high level of universal care.
The advantage of eradicating those mixes over traditional degradation techniques is due to their
living and chemical stability [171-173]. Dye-containing effluents frequently pollute the
environment due to their direct discharge into surrounding water bodies. High intensity
Wastewater is defined as wastewater from dyeing and finishing procedures with a chemical oxygen
demand (COD) concentration greater than 1600 mg/l and a strong dark hue [8, 9]. When this high-
concentration waste water comes into contact with plants near industries, the plants absorb the
toxic pigments through their roots [7]. As a result, it's also a hot topic to figure out how to
breakdown these colors from effluents using simple and low-cost ingredients so that they don't
come into touch with plants. For the removal of dyes from industrial effluents, a variety of
physical, chemical, and biological approaches have been widely used. Adsorption, coagulation,
flocculation, membrane filtration, ozonation, advanced oxidation, liquid-liquid extraction,
biosorption, and other procedures are among them [10- 13]. The majority of these procedures are
energy intensive, non-profitable, and emit waste water that is harmful to the environment [14]. In
terms of starting cost, simplicity of design, ease of operation, and insensitivity to harmful
compounds, adsorption is considered to be the most effective and optimal technology for
wastewater treatment. Despite the fact that activated carbon is an effective adsorbent for organic
pollutants due to its increased adsorption capacity, the higher cost of treatment and challenges with
regeneration prompted the search for less expensive and easier to regenerate adsorbent materials
[15-17]. For the removal of dyes, various adsorbents have been used, such as naturally occurring
materials, biomaterials, industrial waste, agro-waste materials, polymers, and so on. Zeolitic
imidazolate frameworks (ZIFs) are a subclass of metal-organic frameworks (MOFs). Similar to
MOFs, their structures are built from organic linkers and inorganic nodes. Zeolite-like imidazole
skeleton materials (ZIFs) are generated by reaction in solvent with Zn or Co as metal source and
imidazole or imidazole derivatives as organic linkers. They not only inherit the structural
advantages of MOFs, but also overcome the shortfalls of poor thermal and chemical stability of
MOFs to a certain extent. Since their discovery in 2006, ZIFs have been applied to many fields
due to their outstanding properties. ZIF-8 is a typical member of ZIF analogues and the team of
Chen group first synthesized it and named MAF-4 at that time [E11]. Later, the Yaghi’s research
group conducted a systematic study on it and officially named it ZIF-8 [E12]. Compared with other
MOF materials, the synthesis strategies of ZIF-8 are easier and richer. ZIF-8 also has high chemical
and hydrothermal stability that greatly profits from its structure formed by robust links. Taking its
structural stability as an example, ZIF-8 can still maintain structural stability when the temperature
is upto 400°C [E13]. Further, ZIF-8 can also keep its crystallinity and porosity after being put into
various solutions, such as water and organic solvents. It has easily tailorable pore sizes and
structures, which is beneficial to its modification. The unique physical structure and chemical
properties of ZIF-8 provide a promising platform for its design and research in numerous sectors
including gas storage and separation, adsorptive and photocatalytic removal of pollutants, drug
delivery and others. As a consequence, ZIF-8 has become a trendy research hotspot in current
world of science and technology. However, ZIF-8 always suffers from these shortcomings,
(i) ZIF-8 nanoparticles tend to aggregate in water leading to the increase of particle size
and transfer resistance, and the reduction in interfacial area, thus reducing their
adsorption performances.
(ii) ZIF-8 shows weak response to visible light due to its large band gap, and then influence
its solar radiation efficiency.

Furthermore, with the increasing demand for functionalized materials, the application of ZIF-8
monomer is greatly limited. However, to overcome these shortfalls, new multifunctional
composites or hybrids can be formed through the controllable integration of ZIF8 and functional
materials [E14]. These composites or hybrids exhibit superior properties than individual
components through the collective behavior of each functional unit, and have attracted widespread
attention.

The synthesis routes for functionalized ZIF-8 and ZIF-8 composites are quiet simple and very
similar to that for pristine ZIF-8 [E13]. Either pre-synthetic modification or post-synthetic
modification can be carried out to produce funtionalized framework. In case of pre-modification,
more than one type of metal nodes or linkers are used to generate a mixed metal or mixed linker
framework. Conversely, pristine ZIF-8 is prepared and then modified via ligand exchange or
surface alteration for post-synthetic modification procedure.
ZIF-8 and ZIF-8 composites are usually applied to efficiently remove many types of wastewater
pollutants as adsorbants and photocatalysts. These materials have an immeasurable application
prospect in the field of wastewater regeneration. They can reduce dye concentration to ppb levels
due to its higher adsorption capacity and is often much more selective than conventional ion-
exchange resins and commercial activated carbons.

ZIF-8/PANI composite can prepared via a modified interfacial polymerization method which will
enhance the dye adsorption capacity by forming more H-bonds that will result in better dye
removal.

We intend to construct a nanocomposite out of TiO2. In the recent years, the photocatalytic
degradation of various kinds of organic and inorganic pollutants using semiconductors as
photocatalysts have been widely studied [S 30-33]. Among these semiconductors, TiO2 has been
extensively investigated as the most promising photocatalyst due to its high photocatalytic activity,
non-toxicity, high photochemical stability. TiO2 and TiO2 based catalysts give excellent results to
degrade dyestuffs in presence of sunlight [S6]. We are interested in developing a novel
nanocomposite of TiO2 and ZIF-8 for the most efficient removal of textile dyes by both adsorption
and photocatalytic degradation, that is, having the dual nature. However, polymerization of aniline
which is polyaniline (PANI) within the composite can prepared via a modified interfacial
polymerization method which will enhance the dye adsorption capacity by forming more H-bonds
that will result in better dye removal [ACS].

1.2. Environmental issues with textile organic dyes and their damaging effects

As the perspective of people about the quality of water mostly depends on the color of that water,
it becomes more important to remove the color from water first rather than removing the soluble
colorless organic substances. As the new environment regulations have banned the colored effluent
to be discharged in natural water bodies, therefore, an effective and economic treatment of
effluents has become a must [M28].

Dyes are one of the most dangerous types of pollutants, and once they reach the water, they are no
longer good and can be difficult to clean since dyes have a synthetic origin and a complicated
molecular structure, making them more durable and difficult to biodegrade [s34]. High
concentrations of textile dyes in water bodies suffocate the receiving waters re-oxygenation
capacity and block sunlight, disrupting aquatic life and the photosynthesis process of aquatic plants
and algae. Dyes polluting impacts on aquatic ecosystems may also be the result of harmful effects
caused by their long-term persistence in the environment. (i.e., a multi-year half-life),
accumulation in sediments, particularly in fish and other aquatic life forms, breakdown of
pollutants into carcinogenic or mutagenic chemicals, and limited aerobic biodegradability [S35].
According to several toxicological studies, 98 percent of the dyes have a deadly concentration
value (LC50) for fish greater than 1 mg/L, and 59 percent have an LC50 greater than 100 mg/L
[S35]. Dye effluents contain compounds that are carcinogenic and mutagenic to numerous
organisms in addition to being poisonous [S36]. The majority of dyes are non-biodegradable,
carcinogenic, or cause allergies, dermatitis, and skin irritation due to their synthetic nature and
aromatic composition. Furthermore, azo dyes, particularly aromatic chemicals, have acute and
chronic toxicity. Adsorption of azo dyes and their breakdown products (toxic amines) through the
gastrointestinal system, skin, and lungs, as well as creation of hemoglobin adducts and disruption
of blood formation, pose a significant health concern. Aromatic azo dyes have LD50 values
ranging from 100 to 2000 mg/kg body weight [S35]. This is especially dangerous because many
toxins can harm genetic material even if they aren't expressed right away. Azo and nitro chemicals
have been found to be decreased in aquatic body sediments, leading to the formation of potentially
carcinogenic amines. Malachite green has been shown to have effects on the immunological and
reproductive systems, as well as being a potential genotoxic and carcinogenic agent [S36].
Micronuclei are generated as a result of chromosomal breakage (clastogenicity) and aneuploidy.
DNA fragmentation owing to single and double strand breaks was discovered. On human cells,
the dye's genotoxic and cytotoxic effects have also been investigated [S37].

The anionic dye that i have selected is called Remazole Red (RR) that also affect the chain in
aquatic environment and consequently causes an ecological imbalance [M35]. If the discharge of
the textile industry flows over the field, it hardens the soil by clogging the pores of it which
ultimately prevents the penetration of roots [M28]. Besides, the cationic dye that I have selected
is known as Basic yellow 2 (Auramine O) dye, which also exhibits toxic impacts on the aquatic
creatures by means of long lasting effects. The table provided below demonstrates the acute
toxicity level of the selected cationic dye.

Table 1. Acute toxicity level of Auramine O dye. These data are taken from safety data sheet.
 Lethal Dose Concentration Class Exposure time
LC50 3.2 ppm japanese ricefish/ medaka 48 h
(Oryzias latipes)
LC50 1 ppm Poecilia reticulata 96 h

1.3. Bangladesh's current water contamination situation

The textile dyeing and washing sector is vital to Bangladesh's economic development. True, but
they are also producing industrial wastes at the same time. The discharge of industrial waste water
is a big concern in Bangladesh, a growing country, and it has now reached an alarming percentage
[S38, 40]. However, because many factories are located along river banks, undesirable toxic and
hazardous wastes are frequently flushed directly into rivers or ponds without treatment.
Approximately 6000 major and medium companies, as well as 24000 small businesses, discharge
effluents straight into water bodies with no regard for the environment [S41]. According to a
survey published by the Bangladesh Bureau of Statistics (BBS), at least 37.6% of the country's
industrial units lack waste management systems, and 62.1 percent lack waste recycling facilities,
resulting in massive pollution [S42].

For a developing country like Bangladesh, industrialization is an essential prerequisite for faster
economic growth. For several reasons, textiles have become remarkably important part of
Bangladesh economy since the readymade garment industry of Bangladesh started its journey in
the late 1970s. Within a short period of time, it is emerged as an important contributor in the
economy in terms of export earning, empowering women, poverty alleviation and employment
generation. Now it is told and proved to be the number one export earner for the country as the
export value of the textile sector is approximately 28 billion USD per year, which is more than
80% of total national export earnings and 12.26% in the GDP[M36],[M1]. However, this sector is
not about all good as is associated with different environmental issues due to the wastewater
generated by textile industries. The untreated effluents coming out from the most textile industries
are discharged into the rivers with numerous large sources of pollution located outside of the urban
areas, including Tongi, Gazipur Ashulia and Savar [M37-38]. In Bangladesh, in the 2016 the
textile industries produced approximately 217 million m3 of effluent containing wide range of
pollutants and contaminants [M36]. According to the DIFE (Department of Inspection for
Factories and Establishments), the number of conducting garment factories are nearly 3000. So if
the untreated effluent discharge rate is to be continued then it is estimated that this number will
rise to more than 349 million m3 by 2023.

In Bangladesh, most of the industries haven’t any Effluent Treatment Plant (ETP). So, after textile
processing like dyeing, the effluents get directly mixed into the land or river water. These effluents
contain high amount of heavy, medium metal which is already discussed. Normally mordents are
used in dyeing process as a fixing agent. Most of the mordents contain Chromium (Cr).

Under the Bangladesh Environment Conservation Act, 1995, and the Environment Conservation
Rules, 1997, the government designates textile dyeing industries as "Red industries" (the most
polluting), and made Effluent Treatment Plants (ETPs) required for the industries [M41].

In the figure provided below, some images of selected wastewater site in Bangladesh are shown.

Figure 1. Images demonstrating some selected wastewater site in Bangladesh.

1.4. Objective of research

The objectives of this study are to prepare TiO2, ZIF-8, PANI, TiO2 doped ZIF-8 (TiO2@ZIF-8),
and finally x%TiO2@ZIF-8/PANI (where is x% denotes 10, 20 and 30 wt% of TiO2 with respect
to the weight of ZIF-8) composites and evaluate the effect of fabricating composites through series
of adsorption and photodegradation experiments of Remazol red (Anionic dye) as well as
Auramine O (Cationic dye) in aqueous media under natural sunlight irradiation. In the present
work, Titanium (IV) isopropoxide (TTIP), 2-methyl imidazole, Zinc Nitrate Hexahydrate,
Anniline, and Methanol were used as fundamental precursors. Each of the chemicals is cheap and
hence production of photocatalyst in this method can be financially feasible for large scale
production. On the other hand, no specialized instruments are used in the preparation and that
makes the process even more hassle free. Furthermore, investigation of photocatalytic property
was performed under sunlight irradiation which is abundant and feasible to apply on textile
industries effluent.

Therefore, the aims and objectives of this research work are furnished as follows:

1. Synthesis of TiO2, ZIF-8, PANI, and TiO2@ZIF-8 composite.

2. To develop a cost effective and efficient photacalytically active composite TiO2@ZIF-8/PANI.

3. Detailed characterization of synthesized composite using XRD, FTIR, FE-SEM, XPS, UV- Vis
DRS, BET surface area measurements, PL, Zeta potential measurement, and DLS.

4. The photo-degradation efficiency of all synthesized composites with Remazol Red (Anionic)
dye irradiating with UV and sunlight.

5. The photo-degradation efficiency of all synthesized composites with Auramine O (Cationic)

dye irradiating with UV and sunlight.

6. Investigation of photocatalytic degradation reaction mechanism.

7. Studying the effects of numerous factors like pH, pollutant concentration, and contact time on
the removal efficiency.

8. Detailed performance analysis would be investigated by using PANI, ZIF-8, TiO2, TiO2@ZIF-
8 composite as well as TiO2@ZIF-8/PANI composite on dye degradation efficiency.

9. To evaluate the reusability of TiO2@ZIF-8/PANI composite.

10. To investigate the toxicity of the degraded products.

11. Studying further modification and development of the produced composite.

 Chapter 2. Literature Review

2.1. Textile Dyes

A dye is a colored chemical that can be applied to a substrate in an aqueous solution, non-aqueous
solution, or aqueous dispersion to give it a colored look. To obtain varied hues, all organic dye
compounds have unsaturated groups that absorb light (in the visible spectrum: 400-800 nm) at
different wavelengths. Because the electrons are more mobile to generate resonance, unsaturated
groups can absorb lower energy light in the visible spectrum.

Dye molecules are made up of two main components: chromophores, which provide color, and
auxochromes, which can not only replenish the chromophore but also make the molecule soluble
in water and increase its affinity (to attach) to fibers [S44]. Color index (CI) generic names are
assigned to each dye based on its application features and color [S42, 45, 46].

In the figure given below, some images of dyes and dye solutions are provided

Figure 2.1. Illustration demonstrating sample images of dye solutions and dyes.

Dyes aren't all colorful substances. For a colored substance to behave as a dye, two conditions
must be met.

(i) Presence of chromophores: These are the groups that are responsible for giving a dye its color
by absorbing light in the near ultraviolet range; some important chromophores are: -N-O, -NO2, -
N=N-, -C=O, -C=S, -C=N, (CH=CH)n and so on. Chromogens are substances that include
chromophores.

(ii)Auxochromes: A dye should be light, water, and soap resistant. As a result, it must form stable
chemical bonds with the fibers. Some groups, which could be acidic or basic in nature, establish
these chemical linkages. Auxochromes are such groups, with names like -OH, -COOH, -SO3H
(acidic), -NH2, -NHR, -NR2 (basic), and so on. A chromogen that lacks auxochromes will never
be able to operate as a dye [S47].

The following characteristics should be possessed by dyes used on textile fibers:

• Attractive & stable color i.e. should not undergo structural changes easily.
• Affinity to the fibers.
• Steadily dispersed in water or solvents or soluble in water or any compatible medium.

2.2. Classification of commonly used dyes in the industries

In the textile industries generally, the synthetic dyes are used. In most of the synthetic dyes azo
group is present. Azo dyes account for the majority of all textile dyestuffs produced and has been
the most commonly used synthetic dyes.

Some properties of dyes classified on their usage are described in details.

(i) Acid Dyes: They are generally water soluble. The principal chemical classes of acid dyes are
azo (including pre metallized), anthraquinone, triphenylmethane, azine, xanthene, nitro and
nitroso.

(ii) Cationic or Basic Dyes: This water-soluble dye yields colored cations in solution and that's
why are called as cationic dyes. The principal chemical classes are diazahemicyanine,
triarylmethane, cyanine, hemi cyanine, thiazine, oxazine and acridine.

(iii) Disperse Dyes: These are substantially water-insoluble non-ionic dyes used for hydrophobic
fibers from aqueous dispersion. They generally contain azo, anthraquinone, styryl, nitro groups.
(iv) Direct Dyes: They are water-soluble anionic dyes and when dyed from aqueous solution in
the presence of electrolytes have high affinity for cellulosic fibers. Generally, the dyes in this class
are polyazo compounds, along with some stilbenes, phthalocyanines and oxazines.

(v) Solvent Dyes: These dyes we solvent soluble (water insoluble) and generally nonpolar or title
polar, i.e. lacking polar solubilizing groups such as sulfonic acid, carboxylic acid ammonium. The
principal chemical classes are predominantly azo and anthraquinone, but phthalocyanine and
triarylmethane are also used.

(vi) Sulfur Dyes: They have intermediate structures and though they form relatively small group
of dyes the low cost and good wash fastness properties make this class important from an economic
point of view.

(vii) Vat Dyes: These water insoluble dyes are with principal chemical class containing
anthraquinone (including polycyclic quinones) and indigoids.

(viii) Reactive dyes: These are a class of highly colored organic substances, primarily used for
tinting textiles that attach themselves to their substrates by a chemical reaction that forms covalent
bond between the molecule of dye and that of the fiber. The dyestuff thus becomes a part of the
fiber and is much less likely to be removed by washing than are dyestuffs that adhere by adsorption.
The first fiber reactive dyes were designed for cellulose fibers, and they are still used mostly in
this way. There are also commercially available fiber reactive dyes for protein and polyamide
fibers. The dyes contain a reactive group that, when applied to a fiber in a weakly alkaline dye
bath, form a chemical bond with the fiber. Reactive dyes can also be used to dye wool and nylon,
in the latter case they are applied under weakly acidic conditions. The most important characteristic
of reactive dyes is the formation of covalent bonds with the substrate to be colored, i.e. the dye
forms a chemical bond with cellulose, which is the main component of cotton fibers. They are
anionic dyeswith a general structure as D-B-G-X,

Where,

D = Dye part or chromogen (color producing part). Dyes may be direct, acid, disperse dye etc.

B = Bridging part. It may be -NH- group or -NR- group.

G = Reactive group bearing part.

X = Reactive group.

The dyes which are used for coloring fabrics can be classified according to their sources-

Natural Dye: These dyes are based on raw materials available in nature (plants, insects, and
minerals) and are non–polluting. Examples are, Saffron, Mehdi, Indigo.

Chemical Dye: These dyes are not received from natural sources. They are synthetically made by
using various chemicals. Chemical dyes are cheap and easy to apply, with overall good color
fastness but cause environmental pollution. Examples are, Acid dye, Basic dye, Azoic dye, Direct
dye, Disperse dye, Reactive dye, Vat dye.

2.3. Dye Removal Technologies

Few decades earlier, the dyes selection, application and use were not given a major consideration
with respect to their environmental impact. Even the chemical composition of half of the dyes used
in the industry was estimated to be unknown. With the growing concern on health mainly on
aesthetic grounds, it was more from 80s that people started paying much attention to the dye wastes
too. In the last few years, however, more information on the environmental consequences of
dyestuff usage has become available and the dye manufacturers, users and government themselves
are taking substantial measures to treat the dye containing wastewaters. Since initially there was
no discharge limit the treatment of dye wastewater started just with some physical treatments such
as sedimentation and equalization to maintain the pH, total dissolved solids (TDS) and total
suspended solids (TSS) of the discharged water. Later secondary treatments such as the use of
filter beds for biodegradation and, more recently, the introduction of the activated sludge process
(aerobic biodegradation) were used to treat the dye wastewater.

Normally industrial-wastewater treatment processes consist of following steps like:

Pretreatment – industrial-wastewater streams prior to discharge to municipal sewerage systems

or even to a central industrial sewerage system are pretreated doing equalization, neutralization;
then they undergo,
Primary treatment and wastewater is directed toward removal of pollutants with the least effort.
Suspended solids are removed by either physical or chemical separation techniques and handled
as concentrated solids; then they are given a secondary treatment usually involving
microorganisms (biological treatment) primarily bacteria which stabilize the waste components.
The third step is physical– chemical treatment or tertiary treatment and the processes included
in this are adsorption, ion exchange, stripping, chemical oxidation, and membrane separations. All
of these are more expensive than biological treatment but are used for the removal of pollutants
that are not easily removed by biological methods. Though these are generally utilized in series
with biological treatment, sometimes they are used as stand-alone processes too. The final step of
the pollutants removal is the sludge processing and disposal. Dye wastewater are also treated in
more or less a similar way, nevertheless, there is no single standard methodology/treatment
procedure used for all types of wastes.

We are classifying the methodologies generally adopted to treat dye wastewater in three categories
and the illustration is provided below:

Figure 2.2. Schematic representation of dye removal technologies from aqueous effluent.
Some of the methodologies lying in above mentioned categories are discussed in brief in
subsequent paragraphs.

2.3.1. Physical methods

The physical treatment of dye effluents includes unit operations of phase separation without any
changes in chemical structure and composition. Some of the most common physical treatment
methods can be described as follows.

(i) Sedimentation

Sedimentation is the basic form of primary treatment used at most municipal and industrial
wastewater treatment facilities. There are a number of process options available to enhance gravity
settling of suspended particles, including chemical flocculants, sedimentation basins, and
clarifiers.

(ii) Filtration technology

Filtration technology is an integral component of drinking water and wastewater treatment

applications which include microfiltration, ultrafiltration, nano-filtration, and reverse osmosis.
This has been investigated for color removal. Each membrane process is best suited for a particular
water treatment function. Among them, microfiltration is of not much use for wastewater treatment
because of its large pore size, and though ultrafiltration and nano-filtration techniques are effective
for the removal of all classes of dyestuffs, dye molecules cause frequent clogging of the membrane
pores making the separation systems of limited use for textile effluent treatment. The main
drawbacks are high working pressures, significant energy consumption, high cost of membrane
and a relatively short membrane life which makes their use limited for treating dye wastewater.
Reverse osmosis forces water, under pressure, through a membrane that is impermeable to most
contaminants. The membrane is somewhat better at rejecting salts than it is at rejecting non-ionized
weak acids and bases and smaller organic molecules generally molecular weight below 200.
Reverse osmosis is effective decoloring and desalting process against the most diverse range of
dye wastes, and has been successfully employed for recycling. The water produced by reverse
osmosis, will be close to pure H2O.
 (iii) Adsorption

The adsorption process has been widely used for color removal. Adsorption is one of the processes,
which besides being widely used for dye removal also has wide applicability in wastewater
treatment. The term adsorption refers to a process wherein a material is concentrated at a solid
surface from its liquid or gaseous surroundings. The history of carbon adsorption in the purification
of water dates back to ancient times. Adsorption on porous carbons was described as early as 1550
B.C. in an ancient Egyptian papyrus and later by Hippocrates and Pliny the Elder, mainly for
medicinal purposes. However, on scientific records the phenomenon of adsorption was observed
by C.W. Scheele in 1773 for gases exposed to carbon [E33]. This was followed by observations
made by Lowitz in 1785 of the reversible removal of color and odor producing compounds from
water by wood charcoal. Larvitz in 1792 and Kehl in 1793 observed similar phenomenon with
vegetable and animal charcoals, respectively [E34]. However, it was Kayser who introduced for
the first time in 1881 the term adsorption to differentiate surface accumulation from intermolecular
penetration. He postulated that the basic feature of an adsorption process is surface accumulation
of material [E35].

Adsorption can be classified in two categories,

(a) Physi-sorption

If the attraction between the solid surface and the adsorbed molecules is physical in nature, the
adsorption is referred to as physical adsorption or physi-sorption. Generally, in physical adsorption
the attractive forces between adsorbed molecules and the solid surface are van der Waals forces
and they being weak in nature result in reversible adsorption.

(b) Chemisorption

If the attraction forces are due to chemical bonding between adsorbate and adsorbent, the
adsorption process is called chemisorption. In view of the higher strength of the bonding in
chemisorption, it is difficult to remove chemisorbed species from the solid surface.

2.3.2. Chemical treatment

Chemical treatment of dye wastewater with a coagulating/ flocculating agent is one of the robust
ways to remove color. The process involves adding agents, such as aluminum (Al3+), calcium
(Ca2+) or ferric (Fe3+) ions, to the dye effluent and induces flocculation. Besides these other agents
have also been used for the process. Sometimes combination of two may also be added to enhance
the process. Generally, the process is economically feasible (but sometimes becomes expensive
due to the cost of chemicals) with satisfactory removal of disperse, sulfur, and vat dyes. However,
the main drawback of the process is that the final product is a concentrated sludge produced in
large quantities also, besides this; the removal is pH dependent. This process is not good for highly
soluble dyes and the result with azo, reactive, acid and especially the basic dyes are generally not
good.

(i) Oxidation

Oxidation is a method in which wastewater is treated by using oxidizing agents. Generally, two
forms viz. chemical oxidation and UV assisted oxidation using chlorine, hydrogen peroxide,
fenton’s reagent, ozone, or potassium permanganate are used for treating the effluents, especially
those obtained from primary treatment (sedimentation). They are among the most commonly used
methods for decolorization processes since they require low quantities and short reaction times.
They are used to partially or completely degrade the dyes (generally to lower molecular weight
species such as aldehydes, carboxylates, sulfates and nitrogen). However, a complete oxidation of
dye can theoretically reduce the complex molecules to carbon dioxide and water. It is worth to
note that pH and catalysts play an important role in oxidation process.

(ii) Ozonation

Ozonation carried out by ozone generated from oxygen has been studied by various workers and
has been found to be a very effective way of decolorizing textile effluents. It studied the ozonation
for color removal (reactive dyes) and found that color removal of the effluent can be achieved in
5 min of contact time for yellow and blue shades at an ozone consumption of 37.5 mg/L and 36
mg/L, respectively and suggested that ozonation is efficient in decolorization of exhausted dye
bath effluents containing conventional reactive dyes. The decolorization of aqueous C.I. reactive
blue 15 was studied by in a semi batch reactor, who found the process to be a pseudo-first-order
reaction with respect to the dye. The authors observed that ozonation also effectively removed
chemical oxygen demand (COD). They suggested that ozonation can be used to remove
completely the color and chemical oxygen demand too to an extent, which is sufficient for water
reuse even in critical conditions as dyeing with light tones.

(iii) Advanced Oxidation Processes (AOPs)

Advanced Oxidation Processes (AOPs) are the processes involving simultaneous use of more than
one oxidation processes, since sometimes a single oxidation system is not sufficient for the total
decomposition of dyes. These reactions, all of which involve the accelerated production of the
hydroxyl free radical, which is very reactive, are termed advanced oxidation processes (AOPs) and
include techniques as Fenton’s reagent oxidation, ultra violet (UV) photolysis and sonolysis. They
are capable of degrading dyes at ambient temperature and pressure and may also have an advantage
over biological treatment for waste streams containing toxic or bio-inhibitory contaminants. The
central attraction of advanced oxidation processes is that organic contaminants are commonly
oxidized to CO2. A wide variety of advanced oxidation processes are available like chemical
oxidation processes using ozone, combined ozone and peroxide, ultra violet enhanced oxidation
such as UV/hydrogen peroxide, UV/ozone, UV/air wet air oxidation and catalytic wet air oxidation
(where air is used as the oxidant). Nevertheless, in general AOPs have the drawback of producing
some undesirable by-products, complete mineralization is not possible and the process is pH
dependent. Also, depending on the process the limitation may vary, e.g., in the process involving
color removal by the UV/H2O2 treatment the important factors that influence color removal are
peroxide concentration, time of treatment, intensity of UV radiation, pH, chemical structure of the
dye and dye bath additives. Though the advanced oxidation processes have proven potential and
found technically sound for color removal they are quite expensive especially for small-scale
sector of developing countries.

(a) Photocatalysis

Photocatalysis is the acceleration of photoreaction in the case when there is a catalyst and light. In
this process, photocatalyst decomposes the toxic and hazardous compounds but the catalyst is not
consumed in the chemical reaction. When a photocatalytic material is exposed to light, it absorbs
photon energy and, as a result, various chemical reactions occur. The driving force of
photocatalysis by semiconducting particles is the excess free energy of electron hole pairs
generated in the particles by this light absorption. When a semiconductor is illuminated with
photons of energy higher than or equal to its band gap, photoelectrons, e- and photo-holes, h+ are
created. If the semiconductor is immersed in water, for example, the holes react with water
molecules (H2O) or hydroxide ions (OH-) and produce free hydroxyl radicals (OH•). These
hydroxyl radicals (OH•) are very strong oxidants and capable of oxidizing many dyes and other
organic compounds. Whereas OH- has a charge of -1, the charge of OH• is zero; and OH• needs an
electron in order to achieve stability [E36]. Although direct reactions of holes and organic
molecules as well as other direct and indirect reactions may occur, hydroxyl radical oxidation is
thought to be the primary mechanism for destruction of organic compounds. The OH- radicals
oxidize hydrocarbons and other water insoluble organic compounds to water soluble ones such as
ketones, aldehydes, carboxylic acids, etc. and ultimately to CO2. On the other hand, photo
generated electrons can react with dissolved O2, to produce superoxide anion (O2-) which also
takes part in degradation reaction. The ultraviolet (UV) radiation used in photocatalysis may come
from the sun or an artificial source.

2.3.3. Biochemical treatment

Biological treatment is the most common and widespread technique used in dye wastewater
treatment. A large number of species have been used for decolorization and mineralization of
various dyes. The methodology offers considerable advantages like being relatively inexpensive,
having low running costs and the end products of complete mineralization not being toxic. The
process can be aerobic (in presence of oxygen), anaerobic (without oxygen) or combined aerobic–
anaerobic.

(i) Aerobic treatment

Bacteria and fungi are the two microorganism groups that have been most widely studied for their
ability to treat dye wastewaters. In aerobic conditions, enzymes secreted by bacteria present in the
wastewater break down the organic compounds. The work to identify and isolate aerobic bacteria
capable of degrading various dyes has been going on since more than two decades. microorganisms
including Rhyzopus oryzae, Cyathus bulleri, Coriolus versicolour, Funalia trogii, Laetiporous
sulphureus, Streptomycessp, Trametes versicolourand other microorganisms have also been tested
for the decolorization of dyes. Various factors like concentration of pollutants, dyestuff
concentration, initial pH and temperature of the effluent, affect the decolorization process.

(ii) Anaerobic treatment

The potential of anaerobic treatment applications for the degradation of a wide variety of synthetic
dyes has been well demonstrated and established by. Though some efforts in the recent past to
decolorize dyes under aerobic conditions have met with success the general perception of
nonbiodegradability of most azo dyes in conventional aerobic systems still persists. Since its
investigations from early 1970s on anaerobic decolorization of azo dyes various successful studies
have been reported. An anaerobic pretreatment step could be a cheap alternative compared with
aerobic systems as expensive aeration is omitted and problems with bulking sludge are avoided.
In addition, environmentalists suggested, the advantages of anaerobic treatment to be that dyes can
be reductively decolorized with the efficient and cheap removal of BOD levels, heavy metals can
be retained through sulfate reduction, no foaming problems with surfactants, high effluent
temperatures can be favorable, high pH effluent can be acidified and degradation of refractory
organics can be initiated (e.g., surfactants, chlorinated aromatics). Nevertheless, the drawbacks
were suggested to be that BOD removal can be insufficient, dyes and other refractory organics are
not mineralized, nutrients are not removed and sulfates give rise to sulfide.

(iii) Combined aerobic–anaerobic treatment

In order to get better remediation of colored compounds from the textile effluents, a combination
of aerobic and anaerobic treatment is suggested to give encouraging results. An advantage of such
system is the complete mineralization which is often achieved due to the synergistic action of
different organisms. Also, the reduction of the azo bond can be achieved under the reducing
conditions in anaerobic bioreactors and the resulting colorless aromatic amines may be mineralized
under aerobic conditions, thereby making the combined anaerobic–aerobic azo dye treatment
system attractive. Thus an anaerobic decolorization followed by aerobic post-treatment is
generally recommended for treating dye wastewaters. Generally, the factors like concentration of
dyes, initial pH and temperature of the effluent, affect the decolorization process. Though this
methodology is cost-competitive, and biological treatments are suitable for variety of dyes, the
main drawbacks of the biological treatment is low biodegradability of the dyes, less flexibility in
design and operation, larger land area requirement and longer times required for decolorization
fermentation processes thereby making it incapable of removing dyes from effluent on a
continuous basis in liquid state fermentations.

2.3.4. Electrochemical methodology

Electrochemical methodology as a tertiary treatment is also used to remove color. Decolorization

can be achieved either by electro oxidation with non-soluble anodes or by electro-coagulation
using consumable materials. Several anode materials, like iron, conducting polymer a boron doped
diamond electrode etc., with different experimental conditions, have been used successfully in the
electro-degradation of dyes. A color removal of 83–100% was observed for Direct Red 80 using
three different electrodes: iron, polypyrrole doped with chromium and boron doped diamond
electrode. This technique is effective in decolorization of soluble and insoluble dyes with reduction
of COD. It is worthwhile pointing that among other variables the rate of color and organic load
removal depends, on the anode’s material and the working potential.

2.4. Adsorbent

An adsorbent is a porous material with a large surface area that can absorb liquids. Intermolecular
forces adsorb substances to its surface. There are a variety of adsorbents that can be used.

2.4.1. Reasons for chosing MOF

Over the last five decades, porous materials (macroporous, mesoporous, microporous or
nanoporous) have drawn research interest of scientists and researchers all over the world. Their
special inherited characteristics such as high surface areas, large pore volumes and tuneable pore
sizes are significantly crucial for fundamental research and practical applications including
adsorption, gas separation, gas storage, catalysis and sensing. [E1-3] Structurally well-ordered
porous materials with high textural properties are generally good hosts in storage of energy related
gases such as carbon dioxide, hydrogen, methane with high capacity, selectivity and regenerability.
They also have the potential to light up portable electronic devices for electrochemical energy
storage and conversion.
Metal-organic frameworks (MOFs), also known as porous coordination polymers (PCPs), are a
recent class of hybrid materials that have attracted considerable attention during the last few
decades. Their crystalline structure, constructed from the association of inorganic or secondary
building units (metal nodes or oxo-cluster of metal atoms) connected through complex organic
linkers (bi- or multipodal), can be wisely and finely tuned in terms of the chemical nature of
constituents, pore size (micro- or mesoporous), and the shape or type of cavities (cages or channels
and triangular, square or hexagonal, etc.). Strong covalent bonds and intermolecular inteactions
among structural units enable MOFs to have rigid and definite crystal structures. They are more
suitable for above mentioned applications because of having several advantages over conventional
naturally occurring porous materials,

• Only an appropriate solvent can act as templates or directional agents in case of MOF
synthesis whereas specific organic or inorganic templates are vital for commercially
developing naturally occurring zeolites or other porous substances.
• Only a few specific elements for example Si, Al and P can be used to prepare zeotype
materials; that limits the possible number and structures. On the other hand, enormous
number of structure is possible for MOFs because of great variation in metal clusters and
organic linkers.
• Furthermore, a great structural diversity of MOFs can be easily achieved using the same
building blocks, simply by changing the experimental conditions.

As a consequence, the versatile and tunable characteristics of MOFs have, nowadays, made them
very promising candidates for various applications including gas storage, molecular separation,
biomedicine, sensing, catalysis, water-harvesting, and so on [4]. A typical framework structure of
commonly known metal-organic framework, MIL-101 (Cr/Fe) is shown in the next figure,
 Figure 2.3. Typical metal-organic framework

[MIL-101, Fe3(O)/Cr3(O)X(bdc)3(H2O)2]; (bdc = benzene-1,4-dicarboxylate, X = OH or F)

The chemistry and logic behind controllable cavity size can be attributed to a special branch of
molecular science i.e., the reticular chemistry. It defines a special property to form a series of
analogues by varying the linker’s size. It is concerned with making and breaking bonds in
molecules in a controlled fashion, as well as incorporating flexibility and dynamics into large
extended structures. In simple words, reticular expansion of a framework structure can be induced
by altering organic linkers of similar functional groups and extended connector size, and thus an
iso-reticular series of frameworks can be produced [E5]. To be more specific, reticular structures
are viewed as being composed of backbone, functionality attached to the backbone, and space
encompassed by this construct. The backbone provides overall structural integrity while the
functionality provides for optimal pore environment. The pores can be adjusted to allow for
molecules of various sizes, shapes and character to be incorporated and potentially transformed.
By linking molecules together into large and extended structures, reticular chemistry has in effect
endowed the molecule with additional properties inaccessible without being linked [E6].
The next figure illustrates the effect of reticular chemistry for controlling pore size and enlarging
surface area without interrupting initial shape and topolography. Only the linkers are altered to
induce such structural effects.

Figure 2.4. Typical examples of isoreticular expansion of metal-organic frameworks, (a) for MOF-
5, (b) for UiO-66, and (c) for Ni(BDP).

Apart from tunable pore size and controllable structure, MOFs are well studied because of their
exceptionally high surface area, greater than 1000 m2/gm in general, that means only 1 gram of
such compound is more than sufficient to cover an entire football stadium [E7]. This unique
property has made it possible for MOFs to act as highly efficient gas carrier and storage. Other
special properties, high crystallinity and porosity, light weight and low density, tunable
topography, multiple and selective affinity, electrical and optical properties, as well as facile and
easy synthesis route, enhance its suitability as a research-worthy discipline and eligibility to
numerous applications. By far, MOFs have been generally prepared via hydrothermal or
solvothermal synthesis routines by electrical heating in small scales, which take reaction time from
several hours to days. Alternative methods are also available to reduce required time without
compromising with crystal structure and yield, such as microwave-assisted, sonochemical,
electrochemical and mechano-chemical methods. Limited synthesis scaleup for industrial
applications have also been conducted. The first successful MOF scaleup was reported for
HKUST-1 or Cu-BTC (BTC stands for 1,3,5-benzenetricarboxylic acid).

Figure 2.5. The summary of MOFs including synthesis route, characteristics and applications. [M]
Another very popular and studied MOF, MOF-5 was scaled-up in 2005. Other related compounds,
for example UiO 66 was reported to be produced commercially using microwave irradiation [E8].

Therefore, number of yearly publication related to MOFs are increasing very rapidly (Shown in
Figure 2.8) since MOFs are considered as emerging materials considering their easy synthesis,
facile modification and potential application.

Figure 2.6. The number of publications regarding MOFs in the period of 1994-2017. (Data are
collected from google scholar)

2.4.1.1. Reasons for chosing ZIF-8

Zeolitic imidazolate frameworks (ZIFs) are a subclass of metal-organic frameworks (MOFs).

Similar to MOFs, their structures are built from organic linkers and inorganic nodes. However,
whereas MOF structures typically consist of linkers bearing chelating functionalities (e.g.
carboxylate, pyrazolate) favoring the formation of polynuclear secondary building units (SBUs),
the imidazole linkers used to construct ZIFs induce the formation of tetrahedral single transition
metal nodes, and therefore the formation of tetrahedral topologies as in zeolites is favored [E9].
The strong interaction between the charged imidazolate linkers and the metal ions, in combination
with the preference for the formation of rigid cages, renders ZIFs highly robust porous materials.

As the name suggests, the structures of ZIFs are closely related to those of zeolites, which is
ascribed to the combination of tetrahedral nodes and bent linkers mimicking the structural features
of zeolites. In ZIFs, the angle between two metal centers bridged by an imidazolate unit is typically
∠(M–imidazolate–M) = 145°, a value close or even identical to that found for the ∠(Si–O–Si)
angle in zeolites. But the O–Si–O distance is 3.1Å compared to the M–IM–M distance of 5.9 Å,
leading to expanded pore sizes for identical topologies in ZIFs [E10].

Figure 2.7. Comparison of ZIFs (a) with zeolites (b) on the basis of bond angle and bond length.

Zeolite-like imidazole skeleton materials (ZIFs) are generated by reaction in solvent with Zn or
Co as metal source and imidazole or imidazole derivatives as organic linkers. They not only inherit
the structural advantages of MOFs, but also overcome the shortfalls of poor thermal and chemical
stability of MOFs to a certain extent. Since their discovery in 2006, ZIFs have been applied to
many fields due to their outstanding properties. ZIF-8 is a typical member of ZIF analogues and
the team of Chen group first synthesized it and named MAF-4 at that time [E11]. Later, the Yaghi’s
research group conducted a systematic study on it and officially named it ZIF-8 [E12]. The
chemical structure of ZIF-8 is shown in the figure provided below,

Figure 2.8. Schematic illustration showing the crystal structure of ZIF-8, where, blue tetrahedral,
gray balls, and yellow spheres indicate ZnN4, C and micropores respectively. Hydrogen atoms are
omitted for clarity.

Compared with other MOF materials, the synthesis strategies of ZIF-8 are easier and richer. ZIF-
8 also has high chemical and hydrothermal stability that greatly profits from its structure formed
by robust links. Taking its structural stability as an example, ZIF-8 can still maintain structural
stability when the temperature is upto 400°C [E13]. Furthermore, ZIF-8 can also keep its
crystallinity and porosity after being put into various solutions, such as water and organic solvents.
It has easily tailorable pore sizes and structures, which is beneficial to its modification.

Again additional materials can be introduced in ZIF8 structure to produce composite frameworks.
To date, ZIF-8 composites have been successfully prepared with active species, such as fibers,
metals, oxides, polyoxometalates (POMs), polymers, graphene, carbon nanotubes (CNTs) and so
on [E15]. They can maintain the original properties and functions of each phases, and also make
up for the limitation of any single phase in application.

These composites can be synthesized via either ship around the bottle or bottle in the ship
approaches. Generally, in-situ synthesis of ZIF-8 is performed in the former method, whereas in-
situ additives preparation is carried out in latter way. In addition, there exists another type of
composite termed as ZIF-8 derived materials. Here, ZIF-8 composites are pyrolysed to generated
ZIF derivatives that possess enormous surface area and voids. As a result, they exhibit even better
performances compared to parent materials in numerous applications.

2.4.2. Reasons for choosing TiO2 as photocatalyst

Heterogeneous photocatalysis appears to be an intriguing approach for the treatment of anionic

and cationic dyes among the AOPs. The most essential argument for using TiO2 as a photocatalyst
is because it exhibits photocatalytic efficiency in both the UV and visible light spectrums, allowing
direct sunshine to be used as a light source. There is no need for artificial lighting. Indeed, titanium
dioxide (TiO2) activation under UV irradiation (l < 390 nm) allows the generation of highly
reactive (.OH) free radicals from water or hydroxide ions, which is a strong oxidizing agent, and
this oxidizing agent oxidizes a large amount of dye molecules adsorbed on the surface of TiO 2
until their total mineralization [S88].

The advantages of photocatalysis include the ability to use solar UV and the ability to employ
ambient temperature. TiO2 is also non-toxic.

2.4.2.1. General properties of TiO2

Titanium dioxide is found in nature as the mineral’s rutile, anatase, and brookite (shown in Figure
2.11), as well as two high-pressure forms, a monoclinic baddeleyite-like form and an
orthorhombic, a-PbO2-like form, both recently discovered at the Ries crater in Bavaria [S89].
Ilmenite ore is the primary source. This is the most common type of titanium dioxide-bearing ore
on the planet. Rutile is the next most prevalent mineral, with a titanium dioxide content of roughly
98 percent in the ore. When heated to temperatures between 600 and 800 °C [S90], the metastable
anatase and brookite phases irreversibly transition to the equilibrium rutile phase. In addition to
rutile, anatase, and brookite, titanium dioxide can be synthesized into three metastable phases
(monoclinic, tetragonal, and orthorhombic), as well as five high-pressure forms (a-PbO2-like,
baddeleyite-like, cotunnite-like, orthorhombic, and cubic phases). L. Dubrovinsky and co-authors
claim that the cotunnite-type phase is the hardest known oxide, with a Vickers hardness of 38 GPa
and a bulk modulus of 431 GPa (near to diamond's value of 446 GPa) under atmospheric pressure
[S91]. Later research, however, found substantially lower values for both hardness (7-20 GPa,
making it softer than typical oxides like corundum Al2O3 and rutile TiO2) [S92] and bulk modulus
(300 GPa) [S93,94]. Titanium oxides are commercially important ores. Other minerals, such as
ilmenite or leucoxene ores, or one of the purest forms, rutile beach sand, can be used to extract the
metal. As rutile impurities are present in star sapphires and rubies, they gain their asterism [S95].
Titanium dioxide is a mineral that can be found in magmatic rocks, hydrothermal veins, and
perovskite weathering rims. In other minerals, TiO2 generates lamellae as well [S96]. Titanium
oxide spectral lines are visible in class M stars, which are cool enough for molecules of this
chemical to form.

The other two mineral forms of titanium dioxide are brookite and rutile. Anatase is one of the three
mineral forms of titanium dioxide. It is always found as small, isolated, and sharply developed
crystals, and, like rutile, a more commonly occurring modification of titanium dioxide, it
crystallizes in the tetragonal system; however, despite the fact that the degree of symmetry is the
same, the interfacial angles of the two minerals are unrelated, except in the prism-zone of 45° and
90°. The angle over the polar edge of the common pyramid of anatase, parallel to the faces of
which there are perfect cleavages, is 82°9', while the corresponding angle of rutile is 56°5212⁄'.
René Just Haüy named the mineral anatase in 1801, after the Greek word anatasis, which means
"extension," because the vertical axis of the crystals in anatase is longer than in rutile. The physical
characteristics of anatase and rutile differ significantly as well: the former is less hard (5.5-6 vs. 6-
6.5 Mohs) and dense (specific gravity about 3.9 vs. 4.2). Anatase is also optically negative,
whereas rutile is positive, and its luster is more adamantine or metallic-adamantine than rutile's.
Anatase crystals can be divided into two sorts or habits. Simple acute double pyramids with an
indigo-blue to black tint and a steely luster are the most prevalent. This type of crystal may be
found in abundance in the Dauphiné town of Le Bourg-d'Oisans, where they are found in granite
and mica-schist crevices with rock crystal, feldspar, and axinite. Similar crystals of microscopic
size can be found in sedimentary rocks including sandstones, clays, and slates, and can be separated
by washing away the lighter parts of the powdered rock.
The second type of crystal has several pyramidal faces and is usually flatter or prismatic in shape;
the color ranges from honey-yellow to brown. Such crystals resemble xenotime in appearance and
were once thought to belong to this species, earning them the nickname wiserine. They are found
adhered to the walls of crevices in the Alps' gneisses, with the Binnenthal near Brig in the canton
of Valais, Switzerland, being a well-known location. There are also naturally occurring
pseudomorphs of rutile after anatase. Although anatase is not a TiO2 equilibrium phase, it is
kinetically stable. Anatase transitions to the equilibrium rutile phase at temperatures between 550
and around 1000 °C, increasing its specific gravity to 4.2. The temperature of this transformation
is highly influenced by the presence of impurities or dopants in the material, as well as the sample's
morphology [S97].

The different forms of TiO2 are exhibited in the given figure

Figure 2.9. Schematic illustration showing the three forms of TiO2 (anatase, rutile, and brookite)
respectively.

Using titania and its composites with other metal oxides and organic molecules, many researchers
have examined the photocatalytic degradation of various dyes. The following are some examples
of decolorization processes,
Al-amin et al. (2016) used commercial anatase titanium dioxide (TiO2) as a photocatalyst to study
the photocatalytic degradation of two model azo dyes, Remazol Orange and Remazol Red. The
impacts of operational parameters on degradation, such as irradiation period, initial dye
concentration, catalyst loading, and pH of solution, were primarily examined. For the optimal
experimental circumstances of both dye concentrations of 10 mg/L with 200 mg/L anatase titanium
dioxide at pH 3.0 and 180 minute irradiation, the highest degradation found for Remazol Orange
and Remazol Red was 91 percent and 85 percent, respectively [S98].

AKMM Hasan et al. (2020) investigated the solar-assisted photocatalytic degradation of organic
pollutants as an efficient technology for the effective treatment of industrial waste water using
TiO2-ZnO-kaolinite ternary photocatalyst. Remazol Red (RR), an anionic azo dye, was used for
photocatalytic degradation at ambient temperature (25°C). The ternary catalyst, which was made
up of 50 percent kaolinite (w/w), 45 percent TiO2 (w/w), and 5 percent ZnO (w/w), degraded RR
to a maximum of 98 percent. The catalyst was discovered to be suitable for long-term, recurrent
use. The probable contribution of hydroxyl radicals to the photocatalytic breakdown of RR [S99]
was validated by mechanistic research using radical trapping studies.

N Chekir, O Benhabiles et al. (2016) studied methylene blue (MB) degradation by TiO2 and ZnO
aqueous suspension using solar energy in a tubular reactor. The primary goal of this study was to
assess the efficacy of two different types of catalysts: titanium dioxide (TiO2) and zinc oxide
(ZnO). The results revealed that using TiO2 as a catalyst allows for good MB degradation, with a
98 percent disposal rate after 270 minutes and a TiO2 concentration of 0.75 g/L. ZnO can
accomplish the same clearance rate, albeit at a considerably lower concentration of 0.025 g/L after
140 minutes [S100].

B Hayati, NMMahmoodi, and colleagues (2015) developed a Dendrimer-titania nanocomposite

(DTN) and tested its dye removal capacity for direct blue 78 (DB78) and direct red 80 (DR80)
(DR80). The effects of pH and adsorbent quantity on dye removal were investigated, as well as
the isotherm, kinetics, and thermodynamics. The nanocomposite's point of zero charge (pHpzc)
was 6.4. The experimental data was best suited by the Longmuir isotherm model. For DB78, the
maximal adsorption capacity of DTN was 1,250 mg/g, while for DR80, it was 990 mg/g. The
kinetic data matched the pseudo-second order model well. Thermodynamic measurements showed
that dye adsorption by DTN was endothermic and spontaneous, and that physisorption occurred
[S101].

M A Habib et al. (2013) investigated nanocomposite ZnO-TiO2 powders with different ZnO/ TiO2
molar ratios that were generated by heating at 600°C and 900°C from its salt/compound. Under
solar irradiation, the nanosized particles were able to decolorize/degrade brilliant golden yellow
(BGY), an azo dye widely used in the textile industry, in water. The effects of several parameters
on photodecolorization were examined, including photocatalyst loading, molar ratio of ZnO/ TiO2,
pH of the solution, initial dye concentration, and irradiation time [S102].

2.4.3. Reasons for choosing PANI:

 Chapter 3. Experimental

3.1. Materials & supplies

The major raw materials needed for present work were Ti precursor salts for preparing doped and
undoped nanoparticles, and ZIF-8 precursors along with exchangeable linker, PANI precursors.
The major raw materials needed for present work were purchased from trusted sources and used
without further purification. Besides, some chemicals were required to facilitate the processing
and to create optimum environments. A list of necessary chemicals can be described as follows:

• Zinc nitrate hexa-hydrate, >98% (for ZIF-8)

• 2-methyl imidazole, 99% (for ZIF-8)
• Methanol, >98.5% (for ZIF-8)
• Anhydrous ethanol
• Anniline (for PANI)
• Ammonium persulfate (for PANI)
• Titanium (IV) isopropoxide (TTIP) (for TiO2)
• Distilled and DI water
• Sodium hydroxide solution, 1N
• Hydrochloric acid solution, 1N
• Remazole red dye
• Auramine O dye

Table 2: List of chemicals with formula and supplier companies

Serial Name of the Chemical structure Name of the
No. chemical supplier
with formula
1. Zinc nitrate Loba Chemie
hexa-hydrate,
>98%
2. 2-methyl Loba Chemie
imidazole, 99%

3. Methanol, Sisco
>98.5% Research
Laboratories
Ltd.
4. Anniline Tokyo
Chemical
Industry Co.
Ltd.
5. Ammonium Sigma Aldrich
persulfate

6. Titanium (IV) Merck-

isopropoxide chemicals
(TTIP)

7. Sodium Tokyo
hydroxide Chemical
solution, 1N Industry Co.
Ltd.
8. Hydrochloric Loba Chemie
acid solution,
1N

9. Anhydrous Sigma Aldrich

ethanol
 10. Remazole red Loba Chemie
dye

11. Auramine O Loba Chemie

dye

3.2. Required instruments

UV VIS Spectrophotometer:

The % removal of dyes from solutions by the nanocomposite was characterized by using a double
beam UV-VIS spectrophotometer of UV-1700 Series.

Fourier Transform Infrared Spectrophotometer (FTIR):

FTIR spectra of the samples were recorded on an IRPestige21 FTIR spectrophotometer (Shimadzu
Corporation, Japan) in the wavenumber range of 4000-400 cm-1.

X-ray Diffractometer (XRD):

XRD spectra of the samples were recorded by an x-ray diffractometer (Ultima IV, Rigaku
Corporation, Japan). Cu Kα radiation was applied to the samples at 40 kV and 40 mA. The scan
range was 10 to 80° with scan speed of 3°/min. The XRD patterns were recorded on the basis of
the principles of Bragg’s law.

Scanning Electron Microscope (SEM):

An analytical scanning electron microscope (JEOL JSM-6490LA, Tokyo, Japan) was used to
observe the morphology of the samples. The instrument was operated at an accelerating voltage of
20 kV in the back scattered electron mode. The samples were examined at three magnifications to
get better insight into the morphology.

Field Emission Scanning Electron Microscope (FESEM):

A field emission scanning electron microscope, FESEM, (model ZEISS, Gemini 1, Sigma 300 VP)
was used to know topographical and elemental information at magnifications of 65000x at an
accelerating voltage (ETH) of 3.0 kV.

Diffuse reflectance spectra (DRS) analysis:

With the UV-3600i Plus UV-Vis-NIR spectrophotometer (Shimadzu Corporation, Japan), the
photocatalysts' diffuse reflectance spectra (DRS) in the 300–650 nm range are investigated.

X-ray photoelectron spectroscopy (XPS) analysis:

Thermo Scientific's photoelectron spectrometer was used to perform X-ray photoelectron

spectroscopy (XPS) measurements using Al Kα (monochromatic, 1486.6 eV) radiation (UK).

Zeta potential (ζ) analysis:

Zeta potential (ζ) measurements were made for point of zero charge (pHPZC) determination using
"Nano PARTICA sz-100V2 series" HORIBA Scientific Ltd., Japan.

Photo luminescence (PL) analysis:

F-7000 FL Spectrophotometer instrument has been utilized to find out the photo luminescence o
the fabricated composite at an excited wavelength of 350.0 nm with sensitivity 1.

Brunauer-Emmett-Teller (BET) analysis:

Specific surface area, total pore volume and average pore diameter were determined by absorbing
N2 on adsorbent surface using BET sorptometer (BET-201-A, PMI, USA).

Electric balance:
A digital electric balance (D99-09-030 Precisa Gravimentrics AG, Dietilkcn, Switzerland) was
used to measure the weight of the solid chemicals.

Hot plate magnetic stirrer:

A hotplate stirrer LMS-1003 (Daihan Labtech Co. Ltd., Seoul, Korea) was used for heating and
stirring operations.

Sonicator:

To ensure better mixing of chemicals in solutions, a sonicator (Power Sonic 505, 5.7 L, Hwashin
Technology Co., Korea) was used. The ultrasonic sound releases an enormous energy which
disrupts molecular interactions such as interactions between molecules of water, separates clumps
of particles, and facilitates mixing.

Drying oven:

A digital drying oven DO-150 (Han Yang Scientific Equipment Co. Ltd. Seoul, Korea) was used
for the synthesis of the hydrogel and all kind of drying operation.

Demineralization plant:

A demineralization equipment (WDA3000.RW1.5 International Ltd, UK) was used to obtain

demineralized water.

Water still:

Distilled water was collected from a distillation plant (WDA3000.RW1.5, Fistreem International
Ltd, UK).

The pH meter:

A microprocessor pH meter ( pH 211) manufactured by Hanna Instruments was used to monitor

the hydrogen ion concentration of the dye solutions. It was needed to figure out optimum operating
conditions for dye removal experiments.

Centrifuge:
A centrifuging equipment (ZENTRIFUGEN, D-78532) was used to separate the synthesized
products after the completion of reaction. Repeated centrifugation and washing aided to provide
pure products. This equipment was also used for separating adsorbents and catalysts after either
experiments of adsorption and photocatalysis.

Shaker:

A shaker (SK-O330-Pro) manufactured by SCILOGEX was used for solid particles settlement
purposes.

3.3. Preparation of TiO2@ZIF-8/PANI

3.3.1. Preparation of ZIF-8:

Though several routes of synthesizing ZIF-8 have been established, hydrothermal and solvo-
thermal methods, that are based on solvent used are most popular. In this experiment, solvothermal
process has been chosen to prepare ZIF-8. The precursor solutions were simply mixed together in
this experiment, and proper contact was allowed between them for a certain period of time. The
framework formation reaction can be schematically represented as shown in figure,

Figure 3.1. ZIF-8 synthesis reaction from zinc nitrate hexahydrate and 2-methylimidazole.

Solvents except water are used with reactants like Zn source and 2-methylimidazole (Hmim). Here
several organic solvents are used such as methanol; DEF (N,N-diethylformamide), DMF (N,N-
dimethylformamide) as well as mixture of solvents. As maintaining high temperature requires high
energy consumption following a costly process, ZIF-8 was then prepared in room temperature
using Zn ion and Hmim in methanol solution with the formation of rhombic dodecahedral crystal.

The procedure is given as follows, ZIF-8 was synthesized by mixing two separated solutions of
zinc nitrate hexahydrate (Zn(NO3)2 • 6H2O, 2.9g, 9.7 mmol) (Solution A) and 2-methylimidazole
(mim, 6.9 g, 84 mmol) (Solution B), which is dissolved in 100mL methanol. Solution B (Hmim)
was rapidly added to Solution A and then the reaction was allowed to occur at for two hours at
30°C with continuous stirring. Centrifugation was used to separate the ZIF-8 white precipitates,
which were then cleaned with methanol. Purification process was carried out three times to obtain
better result. After being activated at 180°C for 12 hours under reduced pressure, the generated
ZIF-8 resultants were dried at 70°C for overnight [T63][65][66].

Figure 3.2. Schematic representation of flow diagram for ZIF-8 synthesis.

3.3.2. Preparation of PANI:

Among numerous procedures of preparing PANI, I have followed a specific procedure in

accordance with a previous study [Microscale Hierarchical Three-Dimensional Flowerlike
TiO2/PANI Composite: Synthesis, Characterization, and Its Remarkable Photocatalytic Activity
on Organic Dyes under UV-Light and Sunlight Irradiation]. The desired amount of aniline which
was 1mL was dissolved in 40 mL of a HCl (1N) solution and termed as A, we then stirred them
for another hour. After that, 20 mL of a HCl (1 N) solution containing APS ((NH4)2S2O8) with an
equimolar ratio of aniline was then slowly added dropwise to a well-dispersed suspension with
continuous stirring at 0 °C in an ice-water bath. After 8 h, an ideal degree of polymerization was
gained, and the dark-green precipitate was obtained after centrifugation. Then the precipitate was
washed repeatedly with ethanol and deionized water. Finally, fine dark-green powders were
achieved by drying the as obtained precipitate in vacuum at 60 °C for 12 hr.

Figure 3.3. Schematic representation of flow diagram for powered PANI synthesis.

3.3.3. Preparation of TiO2:

TiO2 nanoparticles were synthesized using a sol-gel method. Figure 3.4. represents the synthesis
process used for the fabrication of TiO2 nanoparticles.

At first, 10 mL of Titanium (IV) isopropoxide (TTIP) was added dropwise into a homogeneous
mixture of 40 mL ethanol and 5 mL of DI water. It was kept stirring for 20 minutes and the mixture
was kept stirring. The reaction mixture will be kept at 50°C for 3h under agitation followed by the
evaporation of ethanol. The sample was dried at 80°C for 30 minutes. Then the precursor was
calcined for 3 h at 450 °C in an air atmosphere.

Figure 3.4. Schematic representation of flow diagram for anatase TiO2 synthesis.

The reactions for synthesizing TiO2 from TTIP has been provided as follows
Figure 3.5. Synthesis reaction for the preparation of TiO2 nanoparticles from TTIP via sol-gel
method [F56]

3.3.4. Preparation of ZIF-8/PANI composite:

In order to prepare ZIF-8/PANI composite, at first ZIF-8 needs to be prepared as aforementioned.

This controlled interfacial polymerization at ZIF-8 was prepared via post synthetic modification. First,
taking 200 mg of ZIF-8, in 100ml methanol by water bath sonication for 30 minutes. Then about
1 ml of aniline was added to ZIF-8 suspension. The resultant solution was constantly stirred in a
hot plate magnetic stirrer, maintaining temperature at 0°C in an ice bath.

After that, 15 mL of a HCl (1 N) solution containing 0.8 gm APS ((NH4)2S2O8) with an equi-molar
ratio of aniline was then slowly added dropwise to a well-dispersed suspension with continuous
stirring at 0 °C in an ice-water bath. After 8 h, an ideal degree of polymerization was gained, and
the dark-green precipitate was obtained after centrifugation [ACS paper]. Then the precipitate was
washed repeatedly with ethanol and deionized water. Finally, fine dark-green powders were
achieved by drying the as obtained precipitate in vacuum at 60 °C for 12 hr. In order to gather
stability, the composite has been activated at 180°C for 12 hours under reduced pressure.
Figure 3.6. Schematic representation of flow diagram for ZIF-8/PANI composite synthesis.

3.3.5. Preparation of TiO2@ZIF-8/PANI composite:

Several approaches were considered for the preparation of TiO2@ZIF-8/PANI, for example in-situ
nanoparticle or in-situ ZIF-8 synthesis at the surface of nanoparticles and then post synthetic
modification for interfacial polymerization. The first approach was in-situ TiO2 formation in
already prepared ZIF-8/PANI composite. It was not successful since the high calcination
temperature degraded the framework structure.

Another approach was taken for preparing ZIF-8 at the surface of nanoparticles to produce
TiO2@ZIF-8 and then allow control interfacial polymerization reaction in second step. The first
step was successful. However, TiO2 were precipitated during control interfacial polymerization
reaction. Hence another method was needed for successful composite formation.

The last method succeeded where, at first ZIF-8/PANI composite has been fabricated as
aforementioned. Then, they were dispersed in 100 ml methanol, and was sonicated for 30 minutes
in water bath. Then, the prepared anatase TiO2 utilizing the sol gel method aforementioned, were
loaded on 10%, 20%, and 30% mass basis of ZIF-8/PANI, i.e., 20mg/40mg/60mg of TiO2were
added to 200mg of ZIF-8/PANI for these 3 compositions respectively.

The TiO2 did not participate in chemical reactions instead entrapped inside the framework’s cavity
and also forms metal coordination bond with Zn which will be discussed in XPS. A schematic
representation of TiO2@ZIF-8/PANI, 3D nanocomposite preparation is illustrated in figure 3.7.
Figure 3.7. Schematic representation of flow diagram for TiO2@ZIF-8/PANI composite synthesis.

3.4. Conditions for adsorption & catalysis

3.4.1. Properties of Remazol Red and Auramine O

In this experiment, one cationic dye (Auramine O) and one anionic dye (Remazol Red) were
chosen as targeted pollutants for environmental remediation of wastewater. While cationic dyes
possess positively charged species when dissociated in aqueous solution, anionic dyes contain
negatively charged radicals in aqueous solution. Thus by selecting one from each categories helps
understand the effectiveness of synthesized nanocomposite as versatile adsorbent and
photocatalyst.
 (a)

(b)
Figure 3.8. - The chemical structure of (a) Remazol Red and (b) Auramine O dye

Auramine O is a hydrochloride obtained by combining 4,4'-carbonimidoylbis (N,N-

dimethylaniline) with one molar equivalent of hydrogen chloride. A fluorescent stain for
demonstrating acid fast organisms in a method similar to the Ziehl Neelsen. It also can be used to
make a fluorescent Schiff reagent. It has a role as a fluorochrome and a histological dye. On the
other hand, remazol red is a synthetic azo dye with vinyl sulfone functional group. This reactive
dye is chemically known as naphthalene-1-azo-2-Methoxyphenylsulfonylethanedisulfonicacid.
The widely uses of this dye is due to its ability to produce bright shades of wide range, high leveling
quality, good washing fastness and good light fastness. This dye was collected from a local textile
industry of Bangladesh.
Some common properties of both dyes are listed in the given table.
Table 3: General properties of AO & RR dyes:
Property Auramine O (AO) Remazol red (RR)
CAS no. 2465-27-2 11099-79-9
Trade name Auramine O Remazol red
Other name Basic Yellow 2 Reactive Red 21
Molecular weight (g/gmol) 303.83 1120.3
Color Yellow Dark Red
Physical state Crystals or powder Crystals or powder
Solubility Soluble in water Soluble in water
Maximum wavelength, 434 nm 519 nm
λmax (nm)

3.4.2. Preparation of standard dye solutions:

To carry out adsorption and photocatalytic experiments, solutions of both dyes (RR and AO) were
initially made using distilled water. At first, stock solutions of 500 ppm were prepared by adding
125 mg of solid dyes in 250 ml distilled water in two distinct conical flasks. Furthermore, solutions
of varying concentration, for example, 10 ppm, 20 ppm, 30 ppm and 40 ppm, and 50 ppm were
prepared by diluting the stock solutions. The λmax of the dye solutions were calculated using UV-
Visible Spectrophotometer and the pH of the solutions were recorded using a pH meter.

3.4.3. Fixation of λmax & Callibration of dye solutions:

After preparing the dye solutions, next step was to figure out the wavelength at which highest
absorption of radiation was observed and then to create a calibration curve for a number of dye
solutions of different concentrations. This calibration curve would make further experiments
convenient to conduct and analyze. For this purpose, a number of dye solutions of different
concentrations were prepared and then UV-Visible absorbance spectra for each solution were
recorded. The wavelength of radiation at which maximum absorbance found was termed as λmax.
Then, a plot of absorbance versus concentration of dye solution at that fixed wavelength (λmax)
was drawn. This is also called the calibration curve of dye solutions at λmax. Similar procedure
was followed for Remazol red and Auramine o dyes. The λmax value for RR and AO were detected
at 519 nm and 434 nm respectively. The graphical illustration of maximum wavelength and
calibration curve is as follows.

(a) (b)

Figure 3.9. (a) UV-Visible spectrum of standard AO dye solutions at different concentrations and
(b) Calibration curve of AO dye.
 (a) (b)

Figure 3.10. (a) UV-Visible spectrum of standard RR dye solutions at different concentrations and
(b) Calibration curve of RR dye.

3.4.4. Dye removal experiments:

Batch experiments were performed for determining the % removal of dyes using the
nanocomposite and other samples. Approximately 25 ml of each dye solutions having various
concentrations were taken in 100 ml beakers. Then 5 mg of nanocomposites were added in each
solution and properly mixed using magnetic stirrer at 50 rpm. The pH of the solutions was adjusted
by adding 0.1N NaOH and 0.1N HCl solution dropwise. These mixtures were left in direct sunlight
for one hour and then dye loaded composites were separated from the suspension by centrifugation
for 20 minutes. The residual concentration of dye solutions was determined by taking absorbance
at 434 nm for Auramine O and at 519 nm for Remazol red dyes, respectively. The percentage
removal of dye was calculated using the following formula,

Where, Ao is the initial absorbance of AO or RR

 Ae is the equilibrium absorbance of AO or RR

The similar procedures were repeated for other samples, ZIF-8, PANI, TiO2, ZIF-8/PANI,
x%TiO2@ZIF-8/PANI (where x= 10% ,20%, and 30%).

3.4.5. Radical trapping experiments:

Radical trapping experiments were carried out to investigate the potential contribution from
various active species i.e., hole, superoxide and hydroxyl radicals towards the photocatalytic
degradation of AO and RR as they play vital role under visible light irradiation. In this experiment,
ammonium oxalate (AO) was introduced as hole scavenger, ascorbic acid (AA) as superoxide
scavenger and 2-propanol (2P) as hydroxyl radical scavenger. Different AO and RR removal
experiments were carried out under optimized condition in presence of one of these scavengers
and the percentage removal of these dyes were recorded. For comparison purpose, a separate
experiment was also carried out without any scavenger (WS). The percentage removal of AO, RR
was decreased when a particular scavenger worked and thus it was evident that photocatalytic
degradation process was controlled mainly by that corresponding active species.

3.4.6. TOC analysis:

Total Organic Carbon (TOC) of the initial solution and the solution irradiated under optimized
conditions were measured using a TOC analyzer. Finally, the % reduction in the TOC content of
the irradiated sample was measured using the following formula:

% TOC reduction = (TOCi−TOCf / TOCi) ×100%

Where, TOCi is the Total Organic Carbon (TOC) content of the initial solution in ppb

TOCf is the Total Organic Carbon (TOC) content of the irradiated solution in ppb.

3.4.7. Reusability study of the photocatalyst:

In reusability studies, the catalyst was filtered and collected after each cycle and a fresh AO and
RR dye solution with the same concentration was used. The removal efficiency was investigated
up to fifth cycle [58].
 Chapter 4. Result and Discussion

4.1. Characterization:
4.1.1. X-ray Diffraction (XRD) analysis:

XRD technique was applied to identify the crystallographic structure and crystallite size of the
materials. X-rays can produce constructive interference after reflection from atomic planes within
the crystalline materials. The relationship between the incident and reflected X-rays can be
expressed by Bragg’s formula.

𝑛𝜆 = 2𝑑𝑠𝑖𝑛𝜃

Where, n is an integer, λ is the wavelength of X-rays, d is the inter-lattice spacing, and θ is the
incident angle.

XRD patterns of the samples were recorded by an x-ray diffractometer (XRD Ultima IV, Rigaku
Corporation, Japan) at room temperature. Prior to XRD analysis, the samples were ground into
fine powders using mortar-pestle. Cu Kα radiation (λ= 1.54178°A), from a broad focus Cu tube
operated at 40 kV and 40 mA, was applied to the samples for measurement. The XRD patterns of
the samples were measured in the continuous scanning mode with a scan speed of 3°/min and in
the scan range of 5 to 65°. The samples were examined by plotting the angular position and the
intensities of the resultant diffracted peaks.

The outcome of XRD analysis regarding synthesized frameworks ZIF-8, PANI, TiO2, ZIF-
8/PANI, 10%TiO2@ZIF-8/PANI, 20%TiO2@ZIF-8/PANI, and 30%TiO2@ZIF-8/PANI; is
depicted in figure x.

As expected, the synthesized ZIF-8 displayed diffraction peaks (2θ) at 7.3°, 10.33°, 12.67°, 14.65°,
16.4°, 17.98°, 24.46°, and 26.63°, representing (011), (002), (112), (022), (013), (222), (114), and
(134) crystal planes of the zeolitic structure (MDI-JADE6). Since these characteristic diffraction
peaks are present in synthesized ZIF-8, successful synthesis of zeolitic imidazolate framework
with sodalite topology could be assumed. Similarly, synthesized PANI exhibited diffraction peaks
(2θ) at 22.87° and 25.11° representing (021) and (110) crystal planes [Conducting polymer pani
and ZIF-8/PANI 2]. The peaks centered at 25.24°, 37.76°, 48.08°,53.94°, 55.04°, and 62.82° with
corresponding planes (101), (004), (200), (105), (211), and (204) respectively are associated with
the crystal planes of anatase TiO2 (JCPDS PDF #21-1272).

Besides, no difference in diffraction pattern regarding synthesized ZIF-8/PANI was observed

compared to that of synthesized ZIF-8 except for the peak of PANI at 22.87°, in the (021) plane.
Hence the crystallinity and signature sodalite topology of ZIF-8 were significantly present in this
species, indicating successful synthesis of the ZIF-8/PANI composite.

Figure 4.1. XRD pattern of synthesized frameworks like ZIF-8, PANI, TiO2, ZIF-8/PANI,
10%TiO2@ZIF-8/PANI, 20%TiO2@ZIF-8/PANI, and 30%TiO2@ZIF-8/PANI.

Last but not the least, synthesized nanocomposites 10%TiO2@ZIF-8/PANI, 20%TiO2@ZIF-

8/PANI, and 30%TiO2@ZIF-8/PANI evidently showed similar zeolitic structure with sodatile
topology as obtained for other frameworks. The Xray diffraction peaks were identified at 7.3°,
10.33°, 12.67°, 14.65°, 16.4°, 17.98°, 24.46°, and 26.63°, representing (011), (002), (112), (022),
(013), (222), (114), and (134) respectively; representing the structural integrity [E46-47]. While
this set of peaks proved the presence of ZIF-8 like structure, another set of peaks was also found
at 22.87° representing (021) crystal plane and presence of PANI. Then at 25.24°, 37.76°,
48.08°,53.94°, 55.04°, and 62.82° with corresponding planes (101), (004), (200), (105), (211), and
(204) respectively; presenting existence of TiO2 in this sample. However, at additional peak of
30%TiO2@ZIF-8/PANI composite was seen, in 27.18° at (110) plane indicating TiO2 is also in
the rutile phase (JCPDS PDF #21-1276). The intensity of the anatase (101) peak became stronger
than that of the rutile (110) peak.

The anatase/rutile weight fraction are calculated by the following equation:

𝑋𝑅(%)=100/(1+0.8*𝐼𝐴/𝐼𝑅);

where XR is the weight fraction of rutile, IA and IR are the relative strength of anatase (101) plane
and rutile (110) plane, respectively [F60]. The rutile phase was found to be 19.02%. So, anatase
phase was 80.98%.

The crystallite size has been obtained from the full width at half maximum (FWHM) of the most
intense peaks using the Debye–Scherrer’s equation:

where D is the average size of grains, λ is the wavelength Cu Kα XRD used, β is the full width at
half–maximum, and θ is the Bragg’s diffraction angle [F60]–[62].

Table 4. Average crystallite size measurements for ZIF-8.

SI. No. hkl 2 theta (deg) FWHM (deg) Average D

(nm)
1. 011 7.28883 0.18699 44.44593
2. 002 10.33907 0.17126 48.62789
3. 112 12.67789 0.18899 44.15661
4. 022 14.65804 0.17424 47.99391 43.72315
5. 013 16.40436 0.18562 45.14522
6. 222 17.98586 0.20132 41.71151
7. 114 24.4626 0.21164 40.1001
8. 134 26.63422 0.22666 37.60402
Table 5. Average crystallite size measurements for PANI.

SI. No. hkl 2 theta (deg) FWHM (deg) Average D

(nm)
1. 021 22.87 0.1321 19.95 39.0905
2. 110 25.11 0.197 58.231

Table 6. Average crystallite size measurements for TiO2.

SI. No. hkl 2 theta (deg) FWHM (deg) Average D

(nm)
1. 101 25.24 0.30777 26.16
2. 004 37.76 0.29111 28.63
3. 200 48.08 0.30189 28.67 26.82
4. 105 53.94 0.31256 27.82
5. 211 55.04 0.31028 25.61
6. 204 62.82 0.30712 24. 07
Table 7. Average crystallite size measurements for ZIF-8/PANI.

SI. No. hkl 2 theta (deg) FWHM (deg) Average D

(nm)
1. 011 7.2921 0.1624 51.19579
2. 002 10.38703 0.1618 51.49303
3. 112 12.75484 0.1679 49.72623
4. 022 14.7595 0.17024 49.14633
5. 013 16.52745 0.1509 55.56278 50.56
6. 222 18.12853 0.1832 45.86405
7. 114 24.68549 0.17934 47.36081
8. 134 26.88401 0.15627 54.591
9. 021 22.85347 0.1687 50.1787
Table 7. Average crystallite size measurements for 10%TiO2@ZIF-8/PANI.

SI. No. hkl 2 theta (deg) FWHM (deg) Average D

(nm)
1. 011 7.29666 0.17286 48.0979
2. 002 10.38712 0.16838 49.4807
3. 112 12.75538 0.17301 48.2575
4. 022 14.76295 0.18213 45.93809
5. 013 16.54075 0.17293 48.48531
6. 222 18.12581 0.19513 43.05981
7. 114 24.69696 0.18237 46.57496 47.1789
8. 134 26.88783 0.22097 38.6076
9. 021 22.85362 0.14651 57.78266
10. 101 25.24129 0. 20688 43.205
11. 004 37.76251 0. 20347 43.0983
12. 200 48.08432 0.20215 44.9447
13. 105 53.94785 0.19873 46.84847

Table 8. Average crystallite size measurements for 20%TiO2@ZIF-8/PANI.

SI. No. hkl 2 theta (deg) FWHM (deg) Average D

(nm)
1. 011 7.29427 0.17579 47.2962
2. 002 10.38578 0.16946 49.16537
3. 112 12.75574 0.17451 47.84276
4. 022 14.7632 0.18782 44.54641
5. 013 16.54612 0.17541 47.80014
6. 222 18.12677 0.19012 44.19457
7. 114 24.70018 0.18387 46.19526 46.58950
8. 134 26.88695 0.21084 40.46001
 9. 021 22.86124 0.15261 55.46147
10. 101 25.23891 0. 19688 43.18684
11. 004 37.75987 0. 18347 47.79615
12. 200 48.09012 0.21325 42.60638
13. 105 53.94881 0.20873 44.60418

Table 9. Average crystallite size measurements for 30%TiO2@ZIF-8/PANI.

SI. No. hkl 2 theta (deg) FWHM (deg) Average D

(nm)
1. 011 7.29346 0.17821 46.6539
2. 002 10.39012 0.17001 49.00648
3. 112 12.74251 0.17815 46.86463
4. 022 14.75728 0.17901 46.73849
5. 013 16.54091 0.19689 42.58503
6. 222 18.12671 0.17512 47.98008
7. 114 24.69710 0.18571 45.73731 46.11201
8. 134 26.89251 0.21184 40.26920
9. 021 22.85910 0.15271 55.43344
10. 101 25.25812 0. 20188 42.11953
11. 004 37.76917 0. 16347 53.64531
12. 200 48.08916 0.21536 42.18866
13. 105 53.93957 0.20923 44.49579

4.1.2. Fourier Transform Infrared (FTIR) analysis:

Fourier transform infrared spectroscopy (FTIR) is a powerful technique which is used to obtain an
infrared spectrum by absorption or transmission through a solid, liquid or gas. When IR (infra-red)
radiation passes through a sample, some part of the electromagnetic radiation are absorbed and
some are transmitted. The resulting spectrum shows the characteristics of the sample and also
shows the unique molecular finger-print of the sample. FTIR can measure all infrared frequencies
and subsequently decodes them with the assistance of computer software, and the spectral
information of the sample is then generated.

In our experiment, FTIR spectra were recorded on FTIR 8400S (Shimadzu, Japan) in the
wavenumber range of 4000-500 cm-1 (mild–infrared wave number), resolution: 4 cm-1, scans: 20.
Approximately 1 mg of samples was ground with 100 mg KBr by agate mortar and then pellet was
made from the mixture by applying 80 KN pressure. The outcome of this experiment is graphically
expressed in figure X.

Figure 4.2- Graphical representation of FTIR spectra of synthesized compounds for functional
group analysis.

As expected, the synthesized nanoparticle exhibited a broad absorption of radiation at 500 cm-1 to
800 cm-1, which is characteristic of Ti-O-Ti bond stretching in TiO2 [E48][41][49]. The
synthesized ZIF-8 possessed almost all of its characteristic IR transmittance peaks. The significant
peaks for in-plane bending of imidazole ring, imidazole ring stretching, C-N bond stretching and
C=N bond stretching vibrations were attained at 987.35 cm-1, 1415.03 cm-1, 1144.66 cm-1 and
1584.19 cm-1 respectively [E51][52]. Besides, another peak at 751 cm-1 for stretching and bending
vibrations of Zn-O bond was obvious, whereas out of bending vibrations of C=C at 700 cm-1 was
also visible [53]. In addition, other peak at 3428.96 cm-1 evidently represented the existence of
secondary (-NH-) amine groups in synthesized ZIF-8 samples [E46]. At about 2937.85 cm-1, and
3135.37 cm-1, are attributed to the aromatic and the aliphatic C–H stretch of the imidazole,
respectively. And for 1350-1500 cm-1, entire ring stretching (C=C) occurs [ZIF-8 FTIR]. The
peaks for ZIF-8 are shown below,
Table 10. Summary of FTIR spectral analysis of synthesized ZIF-8.
Wavenumber 700 751.01 987.35 1144.66 1415.03
(cm-1)
Assigned C=C Zn-O In plane C-N bond imidazole
Functional aromatic stretching bending of stretching ring
groups of ZIF-8 bends (out of and imidazole ring stretching
plane) bending
Wavenumber 1453.77 1584.19 2937.85 3135.37 3428.96
(cm-1)
Assigned C=C C=N bond Aromatic C–H aliphatic C–H N-H
Functional stretching in stretching stretch of the stretch of the streching
groups of ZIF-8 entire ring imidazole imidazole

These data are also consistent with the previous reports [ZIF-8 FTIR].

For the case of polyaniline, the following peaks arises as provided,

Table 11. Summary of FTIR spectral analysis of synthesized PANI.
Wavenumber 819.75 1118.71 1489.76 1579.7 2850.79 3446.75
(cm-1)
 Assigned C-H of C-N C=C stretch C=N stretch C-H Primary
Functional aromatic ring bending in benzoid in quinonoid stretching N-H
groups of ring ring streching
PANI

The peaks are agreeable with the previously reported data [Optical Characteristics of
Conductive Polymer Polyaniline PANI-EB].
For ZIF-8/PANI composite, most of the above mentioned peaks have been seen indicating the
successful preparation of binary adsorbent. In terms of the synthesized samples x%TiO2@ZIF-
8/PANI (where x% = 10%, 20%, and 30%, respectively), another peak arose without the
mentioned ZIF-8/PANI composites which is near at 600 cm-1, which is for Ti-O-Ti bond
stretching, indicating the successful doping of TiO2, within the composite. As the wt% of TiO2 is
increased from 10% to 30% the Ti-O-Ti bond stretching peak intensifies.

Table 12. Summary of FTIR spectral analysis of synthesized TiO2@ZIF-8/PANI.

Wavenumber 593.24 701.39 751.01 819.75 987.35 1144.66
(cm-1)
Assigned Ti-O-Ti C=C Zn-O C-H of In plane C-N bond
Functional bond aromatic stretching aromatic bending of stretching
groups of stretching bends (out and ring imidazole
composite of plane) bending ring
Wavenumber 1416.23 1454.53 1584.72 2936.21 3136.57 3429.37
(cm-1)
Assigned imidazole C=C C=N bond Aromatic aliphatic N-H
Functional ring stretching stretching C–H stretch C–H streching
groups of stretching in entire of the stretch of
composite ring imidazole the
imidazole
4.1.3. Brunner-Emmett-Teller (BET) Surface Area analysis:

The Brunauer-Emmett-Teller method (BET) is used to determine the physical adsorption of gas
molecules in solid materials with complicated shapes, such as porous materials. In BET method,
adsorption and desorption isotherms are used to identify the number of gas molecules adsorbed on
the material, as well as the surface areas of the analytes are determined using adsorption-desorption
isotherms by introducing an inert gas in the sample surface. The BET equation (given below)
describes the relationship between the number of gas molecules adsorbed (X) at a given relative
pressure (P/Po).

1 1 𝐶−1 𝑃
= + ( )
𝑃
𝑋[𝑃𝑜 − 1] 𝑋𝑚 𝑋𝑚 𝐶 𝑃𝑜

Where, Xm = the number of molecules or atoms of a gas to form a monolayer

C = a parameter related to heat of adsorption.
In this experiment, N2 gas adsorption isotherms and textural properties of samples were carried
out on a BET Sorptometer, BET-201-A, PMI, USA. The textural properties were determined via
nitrogen sorption at 77K. The surface area was calculated using the BET method based on
adsorption data in the partial pressure (P/Po) range of 0-1. The N2 gas adsorption isotherms for
synthesized ZIF-8, PANI, ZIF-8/PANI, and 20%TiO2@ZIF-8/PANI samples are depicted in
following figure x and the textural properties of these samples are shown in table x.

As illustrated in N2 gas adsorption isotherms, ZIF-8 exhibits the maximum surface area of
1079.544 m2/g, whereas PANI demonstrates minimum surface area of 78.25 m2/g. As the quantity
of gas molecules adsorbed at adsorbent’s surface reduced to certain extents after polymerization
to create ZIF-8/PANI than ZIF-8, demonstrating the surface area of 614.129 m2/g. The surface
area further reduced after 20 wt% of TiO2 incorporation into ZIF-8/PANI composite to 328.724
m2/g. The surface area (SABET) as well as pore volume (PVtot) of the samples decreased in a similar
fashion; 43.11% and 69.54% reduction in surface area in ZIF-8/PANI and 20%TiO2@ZIF-8/PANI
respectively. The BET surface areas of pristine ZIF-8 is reported to be in the range of 600 m2/g to
2100 m2/g depending on the crystal size that could be either in nanometer or micrometer range
[E55-56].
Figure 4.3. The graphical representation of N2 gas adsorption isotherms for synthesized ZIF-8,
PANI, ZIF-8/PANI, and 20%TiO2@ZIF-8/PANI.

In addition, in case of commercial ZIF-8, this value is approximately 1400 m2/g. Since the
molecular weight of ZIF-8/PANI is much higher than ZIF-8 as it contains bulky polyaniline that
would surely occupy more space resulting in reduced surface area and cavity sizes. In a report,
nearly 47% of surface area decreases occur in case of ZIF-8/PANI composites, so the results are
consistent with previous literatures.

Moreover, upto 82.11% reduction in the same parameter is found for introducing commercial TiO2
nanoparticles within pristine ZIF-8 [E57-59]. Therefore, the BET surface areas of the synthesized
materials have values compatible to existing literature.

Table 13: Textural properties of synthesized adsorbents.

Adsorbent SABET (m2/g) PVtot (cm3/g) PVmic (cm3/g)

ZIF-8 1079.544 0.58 0.43
 PANI 78.25 0.18 0.10
ZIF-8/PANI 614.129 0.41 0.27
20%TiO2@ZIF-8/PANI 328.724 0.22 0.14

4.1.4. UV–Vis Diffuse Reflectance Spectroscopy (UV-VIS DRS) analysis:

The study of spectroscopy is the sole method to understand the optical behavior of any substance
in the world and ultra-violet diffused reflectance spectroscopy is one of these most utilized
techniques. This characterization tool is generally used to determine radiation absorption and
reflection spectrum as well as band gap energy for opaque solid materials that cannot be analyzed
via UV-Visible absorption spectroscopy. The basic difference between these two techniques is
based on kind of radiation utilized to detect the optical behavior of the material. While the UV-
Visible absorption spectroscopy is based on transmitted radiation and dilute solution of the solutes,
the reflectance data and uniform thickness and other surface properties are the fundamental of UV-
DRS.

In this study, the UV Vis-DRS analysis of the synthesized compounds in the range of 220nm to
850 nm, was recorded with UV-3600i Plus UV-Vis-NIR spectrophotometer. Prior to this analysis,
the samples were finely ground to ensure uniform surface properties. The reflectance as well as
absorbance spectra of the synthesized samples x%TiO2@ZIF-8/PANI (where x% = 10%, 20%,
and 30%, respectively); are presented in figure X. The composites revealed high reflectance in the
visible wavelength with sharp increase in reflectance at absorption edge at 427.5 nm, 421.2 nm,
and 414 nm for the three samples, respectively.

In order to calculate the band gap energy Eg, Kubelka–Munk theory can be applied. The modified
Kubelka-Munk method is used to convert the reflectance R into the equivalent absorption
coefficient.

F(R) =
Figure 4.4: UV–Vis DRS (a) reflectance (%), and (b) absorbance (%) for three different
compositions of samples x%TiO2@ZIF-8/PANI (where x% = 10%, 20%, and 30%, respectively)
photocatalysts.

Where,

K is the Absorption Coefficient, S is the Back-Scattering Coefficient, R is the reflectance, and

F(R) is the Kubelka-Munk function, which is proportional to the absorption coefficient [Fahim10].

Given that, the absorption coefficient α is,

α=

In this instance, k is the spectral extinction coefficient, and λ is the wavelength of the absorbed
photon. The band gap of the composites can easily be obtained from Tauc equation by
extrapolating the linear slope from the plot of (αhν)n on the ordinate and hν (the photon energy)
on the abscissa. The energy of the optical bandgap is thus obtained by extrapolating this linear
region to the abscissa.

Tauc equation,

F(R) × hν = A (hν − Eg)n

Here, A = The proportionality constant
h = Planck’s constant (6.63 x 10−34 Js−1).
n = denotes the nature of the transition.
For crystalline semiconductors,
n = ½ for direct allowed transitions.
n = 2 for indirect allowed transitions.
As TiO2 exhibits direct allowed transitions n=1/2 was employed for TiO2 bandgap calculation. So,
(F(R)hν)0.5 is plotted on the ordinate and hν (the photon energy) on the abscissa. Figure x shows
the Tauc plot of different compositions of photocatalysts as mentioned before.

The calculated values of bandgap for prepared samples have been shown in Table X and the band
gap values for indirect transitions were in agreement with values reported by other researchers in
literature [12,77].

In case of TiO2 increasing in wt% within the composites, results in a drop in bandgap energy [F12].
The lowest bandgap value 3.08 eV was obtained for 30%TiO2@ZIF-8/PANI where the TiO2
percentage is maximum. As the percentage of TiO2 decreases in the compositions band gap value
also increases. In, 10%TiO2@ZIF-8/PANI, where the TiO2 percentage is minimum, the highest
bandgap value of 3.21 eV was found. For, 20%TiO2@ZIF-8/PANI the calculated value of bandgap
was 3.13 eV. But all the band gap values are lower than the pristine TiO2 (3.2 eV), except
10%TiO2@ZIF-8/PANI. That’s, why we have not chosen 10%TiO2@ZIF-8/PANI. However,
higher charge carrier recombination is also caused by reduced bandgap energy. Because of this,
20%TiO2@ZIF-8/PANI performs better than other composites in terms of degrading organic
contaminants, as 30%TiO2@ZIF-8/PANI have a tremendous high recombination rate on account
of the phase conversion of anatase to rutile.

Table 14: Band gap energy (Eg) for indirect transitions of different three compositions of
x%TiO2@ZIF-8/PANI (where x% = 10%, 20%, and 30%, respectively) photocatalysts.

Photocatalysts Band gap energy (eV)

10%TiO2@ZIF-8/PANI 3.21
20%TiO2@ZIF-8/PANI 3.13
30%TiO2@ZIF-8/PANI 3.08
Figure 4.5: Schematic illustration exhibiting the Tauc plot of different three compositions of
x%TiO2@ZIF-8/PANI (where x% = 10%, 20%, and 30%, respectively) photocatalysts.

4.1.5. Field Emission Scanning Electron Microscopy (FE-SEM) analysis:

Scanning Electron Microscope (SEM) is a type of electron microscope equipped with energy
dispersive system usually images a sample by scanning it with a high energy beam of electron in
a raster scan pattern. The electrons interact with the atoms enabling the sample to produce signals
which contains information about the sample's surface morphology, composition and other
properties such as electrical conductivity.
Field emission scanning electron microscope (FESEM) is a widely used instrumental method for
the analysis of micro and nanoparticle imaging characterization of solid objects. It is one of the
high-resolution electron microscopy techniques which provide information about surface
morphology, textural analysis, monitor size, size distribution of synthesized micro and
nanomaterials. Furthermore, it provides specific information about the purity and the degree of
particle aggregation [F71]. FESEM is a high resolution imaging that can be performed with very
low accelerating voltages. In comparison with SEM, The FESEM offers increased magnification
imaging up to 500,000x and the ability to observe very fine surface features even with small
component materials [F72].

In our work, FESEM images of the samples were recorded using a model ZEISS, Gemini 1, Sigma
300 VP scanning electron microscope in a high vacuum mode and at an acceleration voltage of 3
kV. Samples were mounted using a conductive carbon double-sided sticky tape. A thin coating of
gold was sputtered onto the samples to reduce the effects of charging. The FESEM images of
synthesized samples; ZIF-8, TiO2, ZIF-8/PANI, x%TiO2@ZIF-8/PANI (where x% = 10%, 20%,
and 30%, respectively); are presented in the given figures.

ZIF-8:

In figure x, the FESEM image of the synthesized ZIF-8 was presented (a) with particle size
distribution (b) alongside the FESEM image. First of all, the synthesized zeolitic framework, ZIF-
8 exhibited distorted truncated shape as well as some portion of cubic shape in FESEM analysis.
The shape and morphology of ZIF-8 crystals highly depend on reaction time and proper ratio of
reactants as well as solvent. When the time of reaction is significantly low cubic shape appears
with no truncated edges. Again, if additional time for reaction is allowed, sharp edges of cubic turn
into truncated corners of rhombic dodecahedron [E56].

The particles have some degree of agglomeration. FESEM is carried out at a magnification of
65,000x. ImageJ software was used to calculate the average particle size of nanoparticles.
Figure 4.6: (a) FESEM image of ZIF-8 and (b) Particle size distribution histogram of ZIF-8.

For the calculations of average particle size of ZIF-8, the particles were marked at 25 different
locations and plotted it as a size distribution histogram (Figure x.b.). The average particle size of
the ZIF-8 is calculated to be 126.94 nm, which is also agreeable with previous reports [(The impact
of ZIF-8 particle size and heat treatment on CO2/CH4 separation using asymmetric mixed matrix
membrane)].

TiO2:

In figure x, the FESEM image of the synthesized TiO2 was presented (a) with particle size
distribution (b) alongside the FESEM image. First of all, the synthesized anatase TiO2 exhibited a
spherical shape with good dispersion in FESEM analysis [New route for synthesis of pure anatase
TiO2 nanoparticles via utrasoundassisted sol-gel method], which is agreeable to the previously
reported experiments. Less agglomeration of nanoparticles was also appeared this may be due to
aggregation of primary TiO2 particles at high calcination temperature which is necessary to
accelerate the crystal growth of titanium dioxide. FESEM is carried out at a magnification of
45,000x. ImageJ software was used to calculate the average particle size of nanoparticles.
Figure 4.7: (a) FESEM image of anatase TiO2 and (b) Particle size distribution histogram of TiO2.

For the calculations of average particle size of anatase TiO2, the particles were marked at 30
different locations and plotted it as a size distribution histogram (Figure x.b.). The average particle
size of the anatase TiO2 is calculated to be 49.97 nm, which is also agreeable with previous reports.

ZIF-8/PANI:

In figure x, the FESEM image of the synthesized ZIF-8/PANI was presented (a) with particle size
distribution (b) alongside the FESEM image. In this study, the shape of synthesized ZIF-8/PANI
is close to rhombic dodecahedron with truncated edges, which is agreeable to the previous reports
[In Vitro and In Vivo Human Body Odor Analysis Method Using GO:PANI/ZNRs/ZIF􀀀8
Adsorbent Followed by GC/MS]. In addition, a little quantity of crystals revealed simple cubic
morphology with lower particle size. Though the particle size was distributed over a broad range,
a vast majority (more than 80%) lied within 100 nm to 200 nm; while a minority existed beyond
this boundary. The rhombic dodecahedron with truncated edges indicates that ZIF-8 is present
here. Less agglomeration of nanoparticles was also appeared. FESEM is carried out at a
magnification of 65,000x. ImageJ software was used to calculate the average particle size of
nanoparticles.

Figure 4.8: (a) FESEM image of ZIF-8/PANI and (b) Particle size distribution histogram of ZIF-
8/PANI.

For the calculations of average particle size of ZIF-8/PANI, the particles were marked at 25
different locations and plotted it as a size distribution histogram (Figure x.b.). The average particle
size of the ZIF-8/PANI is calculated to be 157.39 nm.

10%TiO2@ZIF-8/PANI:

In figure x, the FESEM image of the synthesized 10%TiO2@ZIF-8/PANI was presented (a) with
particle size distribution (b) alongside the FESEM image. In this study, dopants reduce the size of
the crystal because the radius of O2- (0.14 nm) [F10], as well as Ti4+ (0.0605 nm) are quite small.
possessed structure and morphology extremely close to the synthesized 10%TiO2@ZIF-8/PANI.
They too revealed truncated rhombic dodecahedron crystals with cubic crystals. Moreover, an
irregular hexagonal ZIF-8 morphology was also observed which shows consistensy with other
reports and TiO2 are perfectly doped in the framework (Metal−Organic Framework/Polyaniline
Nanocomposites for Lightweight Energy Storage).

Figure 4.9: (a) FESEM image of 10%TiO2@ZIF-8/PANI and (b) Particle size distribution
histogram of 10%TiO2@ZIF-8/PANI.

Though the particle size was distributed over a broad range, a vast majority lied within 100 nm to
200 nm; while a minority existed beyond this boundary. FESEM is carried out at a magnification
of 65,000x. ImageJ software was used to calculate the average particle size of nanoparticles. For,
the calculations of average particle size of 10%TiO2@ZIF-8/PANI, the particles were marked at
30 different locations and plotted it as a size distribution histogram (Figure x.b.). The average
particle size of the 10%TiO2@ZIF-8/PANI is calculated to be 140 nm.

20%TiO2@ZIF-8/PANI:

In figure x, the FESEM image of the synthesized 20%TiO2@ZIF-8/PANI was presented (a) with
particle size distribution (b) alongside the FESEM image. The morphology of 20%TiO2@ZIF-
8/PANI composite was found to be similar with 10%TiO2@ZIF-8/PANI, as they too revealed
truncated rhombic dodecahedron crystals, with cubic crystals as well as irregular hexagonal ZIF-
8 morphology.

Figure 4.10: (a) FESEM image of 20%TiO2@ZIF-8/PANI and (b) Particle size distribution
histogram of 20%TiO2@ZIF-8/PANI.

Though the particle size was distributed over a broad range, a vast majority lied within 50 nm to
150 nm; while a minority existed beyond this boundary. FESEM is carried out at a magnification
of 65,000x. ImageJ software was used to calculate the average particle size of nanoparticles. For,
the calculations of average particle size of 20%TiO2@ZIF-8/PANI, the particles were marked at
30 different locations and plotted it as a size distribution histogram (Figure x.b.). The average
particle size of the 20%TiO2@ZIF-8/PANI is calculated to be 139.614 nm, as the wt% of TiO2 has
been increased to 20%, the average particle size decreases.

30%TiO2@ZIF-8/PANI:

In figure x, the FESEM image of the synthesized 30%TiO2@ZIF-8/PANI was presented (a) with
particle size distribution (b) alongside the FESEM image. The morphology of 30%TiO2@ZIF-
8/PANI composite was found to be similar with the other two, as they too revealed truncated
rhombic dodecahedron crystals, with cubic crystals as well as irregular hexagonal ZIF-8
morphology.

Figure 4.11: (a) FESEM image of 30%TiO2@ZIF-8/PANI and (b) Particle size distribution
histogram of 30%TiO2@ZIF-8/PANI.

Though the particle size was distributed over a broad range, a vast majority lied within 50 nm to
150 nm; while a minority existed beyond this boundary. FESEM is carried out at a magnification
of 65,000x. ImageJ software was used to calculate the average particle size of nanoparticles. For,
the calculations of average particle size of 30%TiO2@ZIF-8/PANI, the particles were marked at
30 different locations and plotted it as a size distribution histogram (Figure x.b.). The average
particle size of the 30%TiO2@ZIF-8/PANI is calculated to be 137.97 nm, as the wt% of TiO2 has
been further increased from 20% to 30%, the average particle size decreases.
Figure 4.12. The average particle size observed by FESEM, where 10%T, 20%T, and 30%T
means

10%TiO2@ZIF-8/PANI, 20%TiO2@ZIF-8/PANI, and 30%TiO2@ZIF-8/PANI, respectively.

The average particle size obtained by FESEM using ImageJ software agrees well with the XRD
results.

4.1.6. Dynamic light scattering (DLS) analysis:

Dynamic light scattering is a non-invasive technique for measuring the size of particles and
molecules in suspension. Brownian motion is the random movement of particles due to collisions
caused by bombardment by the solvent molecules that surround them. The technique of dynamic
light scattering measures the speed of particles undergoing Brownian motion,

The speed of the Brownian motion is influenced by,

• Particle size
• Sample viscosity
• Temperature
Viscosity is important in determining the speed of Brownian motion.The temperature must be
accurately known, nowadays it is automatically read back by the software. The temperature needs
to be stable during a measurement. Convection currents in the sample cause non-random
movements which prevents accurate size interpretation. The smaller the particle is, the more rapid
the Brownian motion becomes, the larger the particle is, the slower the Brownian motion becomes.

Velocity of the Brownian motion is defined by the translational diffusion coefficient (D). The
translational diffusion coefficient can be converted into a particle size using the Stokes-Einstein
equation,

𝑘𝑇
𝑑𝐻 =
3𝜋𝑛𝐷

Where,

dH = hydrodynamic diameter,
k = Boltzmann’s constant,
T = absolute temperature,
n = viscosity and
D = diffusion coefficient

For the purpose of this investigation, 20%TiO2@ZIF-8/PANI composite was prepared as a 0.5
mg/mL sample solution by dispersing it in DI water. During the course of the investigation, the
pH was varied from 5.5. The result is provided in the following figure,
Figure 4.13. Schematic illustration demonstrating the DLS analysis of our synthesized
20%TiO2@ZIF-8/PANI composite.

From the DLS data, the average particle size for 20%TiO2@ZIF-8/PANI, was found to be 149.18
nm which shows consistency with the value of average particle size in FESEM analysis.

4.1.7. X-ray Photoelectron Spectroscopy (XPS) analysis:

X-ray Photoelectron Spectroscopy (XPS) is a widely used surface-sensitive spectroscopic analysis

technique because it can be applied to a broad range of materials and provides valuable quantitative
and chemical state information from the surface of the materials. XPS is normally accomplished
by exciting a sample surface with monoenergetic Al Kα x-rays causing photoelectrons to be
emitted from the sample surface (from the top 0 to 10 nm). An electron energy analyzer is applied
to measure the energy of the emitted photoelectrons. The elemental identity, chemical state, and
quantity of a detected element can be determined from the binding energy and intensity of a
photoelectron peak.

In our experiment, XPS was performed using a Thermo Scientific photoelectron spectrometer
(UK) with a mono-chromated Al Kα X-ray source (1486.6 eV) operated at 10 mA emission current
and 15 kV anode potential. The XPS spectrum of synthesized 20%TiO2@ZIF-8/PANI is illustrated
in figure X.

Figure 4.14. The XPS spectrum of synthesized 20%TiO2@ZIF-8/PANI.

This elemental analysis evidently showed the existence of zinc (9.58%), carbon (60.19%), nitrogen
(12.64%), oxygen (12.2%), and titanium (5.39%), where the percentages mentioned on the basis
of number of atoms. These respective elements exhibited characteristic peaks at 1021.45 eV,
284.15 eV, 398.56 eV, 530.86 eV and 459.5 eV, respectively. This composition is strictly valid
for composite’s surface. Again the SEM images and other analysis revealed uniform surface and
homogeneous particles. Hence, the surface composition could also be true for internal structure
with insignificant deviations. Besides, peaks other than the desired ones are rarely noticeable in
the XPS spectrum. Thus, the composite framework could be assumed to possess least amount of
impurities. This statement is compatible with other analysis like XRD and FTIR described in
previous sections. The outcome of XPS analysis is summarized in following table X.

Table 15: The summary of XPS analysis of synthesized 20%TiO2@ZIF-8/PANI.

Elements Peak Binding Energy, eV Atomic percentage %

Zn 2p 1021.45 9.58

N 1s 398.56 12.64

C 1s 284.15 60.19

O 1s 530.86 12.20

Ti 2p 459.5 5.39

In addition, detailed XPS analysis corresponding to individual elements was conducted and
graphically presented in figure X. First of all, zinc is the core metal here that exhibited well-defined
peaks at 1044.5 eV and 1021.45 eV. These peaks were characteristic for 2P1/2 and 2P3/2 orbitals
respectively and supported divalent Zn2+ ions present in ZIF-8 [E67][68]. Two other phases of Zn
were found proving at 1023 eV and 1045.5 eV that belong to (Zn-O) oxides formation of Zn which
is consistent with the FTIR data. This data perfectly agrees with reported literatures.

The next vital element in framework is carbon that is the pith of organic chemistry. This element
possessed 60.19% atoms in surface composition and showed three strong peaks at 284, 284.15,
and 285.7 eV of binding energy. In general, aliphatic carbon atoms bonded to hydrogen atoms
show peak at nearly 284 eV of binding energy, which shows consistency with FTIR data [E67][70].
The latter peak could be held responsible for carbon atoms bonded to nitrogen atoms (C-N and
C=N) [E69].
Figure 4.15. Individual XPS spectra of elements constituting the synthesized 20%TiO2@ZIF-
8/PANI nanocomposite, (a) Zn 2p orbitals, (b) C 1s orbital, (c) N 1s orbital, (d) O 1s orbital, (e)
Ti 2p orbitals.
Here comes our next element nitrogen that is also crucial for framework constituting its mandatory
linkers. The atomic percentage of nitrogen in synthesized framework (12.64%). The nitrogen
present in synthesized framework exhibited a strong peak at 400.2 eV of binding energy. This peak
was found to possess two additional peaks at 400.2 eV and 400.51 eV. These three peaks at 398.56
eV, 400.20 eV and 400.51 eV represented nitrogen atoms bonded with carbon (C=N-C aromatic
ring), hydrogen (N-H) and zinc (N-C) respectively [E70][44] It is needless to say that nitrogen
atoms could be bonded only with these atoms so that no undesired phases of nitrogen were present
in the composite.

Another vital element, oxygen, is not usually present in ZIF-8. The detected oxygen came from
metal oxide nanoparticles, TiO2 incorporated in the composite structure. Therefore, the atomic
percentage of oxygen is only 12.2%. The well-defined peak detected at 530.86 eV was further
resolved into two peaks at 530.49 eV and 531.93 eV by peak fitting. The former resolved peak
was responsible for Ti-O-Ti bonds, whereas the latter one represented coordination bonding
between oxygen and zinc atoms (Zn-O) [E42][71]. As a result, this coordination chemistry
between oxygen and zinc could be held responsible for successful and stable incorporation of metal
oxide nanoparticles within polymerized framework.

The XPS peaks corresponding to last element, Ti was small yet noticeable due to only 20wt%
contribution in synthesized framework. Titanium showed two well-defined peaks at 459.5 eV and
465.2 eV, respectively presenting 2p1/2 and 2p3/2 orbitals [E72]. The atomic percentage of oxygen
is only 5.39% for Ti.

4.1.8. Zeta potential analysis:

The charge that arises at the interface between a solid surface and its liquid medium is known as
zeta potential. As a consequence, zeta potential is a function of the surface charge of the particle,
any adsorbed layer at the interface, and the nature and composition of the surrounding suspension
medium. The zeta potential can be determined experimentally, and because it reflects the effective
charge on the particles' surfaces and is thus related to the electrostatic repulsion between them, it
has proven to be extremely useful in estimating the surface charge and understanding the physical
stability of suspensions.
In suspensions, high zeta potential values (both highly positive and highly negative) suggest that
individual particles are electrostatically repelled from one other. It is commonly accepted that zeta
potential values between -30 mV and +30 mV are adequate to have sufficient repulsive force to
provide improved physical colloidal stability. Due to the van der Waals forces acting on them, a
low zeta potential value can lead to particle aggregation and flocculation which may lead to
instability. Zeta potential of our synthesized composite (20%TiO2@ZIF-8/PANI) at different pH
from 2-10 was studied and the result is provided in the following figure and table.

Table 16. Zeta potential (mV) values of the synthesized composite (20%TiO2@ZIF-8/PANI) at
various pH ranging from 2 to 10.

pH Zeta potential (mV)

2.05 34.22
3.13 38.85
4.02 38.21
5.14 38.17
6.07 31.5
7.1 6.19
8.00 0.31
9.02 -20.79
10.05 -19.88
Figure 4.16. Zeta potential measurements of 20%TiO2@ZIF-8/PANI prepared at different pH
values from 2 to 10.

For the purpose of this investigation, 20%TiO2@ZIF-8/PANI composite was prepared as a 2

mg/mL sample solution by dispersing it in DI water. During the course of the investigation, the
pH was varied from 2.0 to 10.0 as mentioned earlier. According to the findings, which are
presented in Table x and Figure x, the zeta potential values of the composite were found to be
negative from pH value greater than 8.06, with values ranging from -20.79 mV and -19.88 mV as
the pH increased from 9.0 to 10.0. The zero charge point is the point at which the surface charge
of the photocatalyst is zero (pHPZC). When the catalyst is at zero charge point (pHPZC), organic
contaminants are less drawn to it. The resultant pHPZC for our composite was found to be 8.06. As
we decrease from pH from 8.06 to 3, the positive charge on the catalyst surface increases, the
maximum charge was found to be 38.85 mV.
4.1.9. PL study:

The photoluminescence (PL) emission spectrum is usually employed to investigate the

photogenerated carriers trapping and charge transfer efficiency of the photogenerated electron/hole
pairs. The stronger PL intensity indicates the faster recombination speed of the photoexcited
electron-hole pairs. Moreover, a lower PL intensity indicates that more number of excited electrons
is transferred stably through the interface [S79,83].

As mentioned before, we have synthesized our desired photocatalyst taking 3 different

dopantweight % which we have named (10%TiO2@ZIF-8/PANI, 20%TiO2@ZIF-8/PANI, and
30%TiO2@ZIF-8/PANI). For these cases, 10 wt%, 20wt%, and 30 wt% of TiO2 has been doped
with respect to the weight of ZIF-8/PANI composite respectively. The photoluminescence (PL)
spectra of the synthesized photocatalysts 10%TiO2@ZIF-8/PANI, 20%TiO2@ZIF-8/PANI, and
30%TiO2@ZIF-8/PANI respectively, were performed at room temperature in order to study the
separation efficiency of photogenerated holes and electrons. For every case, these composites were
prepared as a 1 mg/ 10 mL sample solution by dispersing it in DI water. PL spectra of the samples
excited at 350 nm are shown in Figure x. The PL spectrum of these photocatalysts show a
significant peak at 708.8 nm. The decrease in PL intensity suggests a slow rate of electron-hole
recombination and long-lived charge carriers. The PL intensity follows the sequence of
30%TiO2@ZIF-8/PANI > 20%TiO2@ZIF-8/PANI > 10%TiO2@ZIF-8/PANI. From the figure, it
has been seen that the minimum recombination rate is for 10%TiO2@ZIF-8/PANI and
20%TiO2@ZIF-8/PANI is slightly higher. However, in 20%TiO2@ZIF-8/PANI composite the wt
% of is TiO2higher, and band gap is also lower than 10%TiO2@ZIF-8/PANI as mentioned in the
UV-VIS DRS spectroscopy characterization. Hence, 20%TiO2@ZIF-8/PANI demonstrates better
photocatalytic activity by taking both the effects of PL study as well as UV-VIS DRS spectroscopy
than the two other synthesized photocatalysts.

The main reason for 30%TiO2@ZIF-8/PANI, to show higher recombination rates is when they are
activated at 180°C, some of the TiO2 anatase is converted to rutile phase as described in the XRD,
and we know the recombination rate of rutile phase is higher than anatase phase.
Figure 4.17: Schematic illustration showing the PL spectra of three different compositions of
x%TiO2@ZIF-8/PANI (where x% = 10%, 20%, and 30%, respectively) photocatalysts.
4.2. Adsorption & photocatalytic performance study – Anionic dye

In order to study the adsorption and photocatalytic performance of the synthesized nanocomposite
(20%TiO2@ZIF-8/PANI) towards anionic dye removal, remazol red (RR) was chosen. This dye
has anionic functional group that exhibits negatively charged characteristics in aqueous solution.
A number of parameters, namely pH, time, and initial dye concentration were considered while
carrying out the study. The result of these batch experiments are briefly described in following
sections.

Initially the application was carried out at normal condition with all the synthesized photocatalysts
to compare their degradation efficiency. Later the photocatalysts with highest degradation
efficiency were optimized and used for the application on the degradation of the anionic dye at
various conditions aforementioned.

4.2.1. Performance of individual species:

Whether the performance of our synthesized composite (TiO2@ZIF-8/PANI) overshadowed that

of its constituent species can only be identified by comparison study of all samples (ZIF-8, PANI,
TiO2, ZIF-8/PANI, TiO2@ZIF-8/PANI), without interrupting the operating parameters. During
this experiment, 20 ppm dye solution was considered as standard in room temperature with a
catalyst dosage rate of 0.2g/L, which means 5mg catalyst. The results are summarized in figure
5.x, utilizing the initial pH of RR dye which was found to be 5.34. The peak intensity reduces due
to the photocatalytic removal of RR dye in presence of photocatalysts and sunlight irradiation.
Experimental data are provided in Table 4.

Experimental condition

Initial concentration: 20 mg/L;

Volume of RR solution: 50 mL;

Photocatalyst amount: 5 mg;

pH: 5.34

Irradiation time: 60 minutes (Sunlight);

Figure 4.18 – Comparative study of the performance of constituent species of synthesized
composites (ZIF-8, PANI, ZIF-8/PANI, TiO2, 20%TiO2@ZIF-8/PANI) towards RR dye removal.
(a) Absorbance spectra of dye solution before and after sunlight irradiation, (b) Dye removal
efficiency (%) and amount of dye removed, qe (mg/g), for individual samples.

As illustrated in above two figures, the synthesized nanocomposite, 20%TiO2@ZIF-8/PANI

demonstrated highest dye removal efficiency, 99.24% & qe value 198.5 mg/g in, only one hour.
So, it can be assumed that both polymerization of aniline and photo-active TiO2 incorporation into
the pristine ZIF-8 contributed towards better dye removal performance. Still, the contribution by
TiO2 is higher because it exhibited better efficiency and qe value (77.43%, and 159.9) than ZIF-8
(59.85%, and 131.02), PANI (34.55%, and 82.9), as well as ZIF-8/PANI (74.89%, and 157.2). The
reasons for the improved visible light harvesting property leads to enhance photocatalytic activities
of 20%TiO2@ZIF-8/PANI are,

• Decreased bandgap energy due to incorporation of TiO2

• Increased adsorption rate through H-bonds due to polymerization of aniline into ZIF-8.
• Reduced photoinduced electron/ hole recombination rate as aforementioned in
PL(Shuvo[68], [86], [87].

Table 17. Adsorption and photocatalytic removal for RR dye under sunlight irradiation by the
synthesized materials

Synthesized Material Removal efficiency (%) qe (mg/g)

ZIF-8 59.85% 131.02

PANI 34.55% 82.9

ZIF-8/PANI 74.89% 157.2

TiO2 77.43% 159.9

20%TiO2@ZIF-8/PANI 99.24% 198.5

Thus the synthesized nanocomposite, 20%TiO2@ZIF-8/PANI was optimized through this study
and further investigations were carried out in following sections.

4.2.2. Effect of different parameters on removal of RR dye:

Removal of dyes or any other pollutants from aqueous solution by any substrate is strongly
controlled by a number of experimental parameters. Some parameters strongly affect the removal
process while some parameters play minor role. To identify the maximum efficiency of a material
for pollutant removal, it is suggested to work with a good number of experimental parameters and
find out the optimum value of each parameter. Among different parameters influencing the dye
removal capacity of our composite, the following important parameters were focused on:

1. pH
2. % of TiO2 in the ternary composite
3. Initial concentration of RR
4. Irradiation time

4.2.2.1. Effect of pH:

The pH of the reaction mixture can have a significant impact on the rate of adsorption and
photocatalytic activity of the catalyst. This is because the size and surface properties of aggregated
nanoparticles are controlled by the pH. Finally, it controls the concentration of reactive hydroxyl
radicals. It can also affect the charge of organic pollutants.

Experimental condition

Initial dye concentration: 20 mg/L

Volume of RR solution: 50 mL

Catalyst amount: 5 mg

pH: 2−10

Sunlight irradiation: 60 min

The concentration of hydrogen ion in aqueous solution is crucial for ionic interaction. Since the
anionic dye removal principle is based on ionic interactions and H-bonds formation with
adsorbent, pH is a significant parameter in this study. Therefore, RR removal experiments using
the synthesized 3D nanocomposite (20%TiO2@ZIF-8/PANI) were performed with a wide range
of pH variation from 2 to 10. The summarized result of these trials is demonstrated in following
figure and table.

Figure 4.19: Study of the effect of pH on RR dye removal performance of 20%TiO2@ZIF-8/PANI

in 20 ppm dye solution with 0.2g/L dosage of adsorbent (a) Absorbance spectra of dye solution
before and after sunlight irradiation for one hour, (b) Dye removal efficiency (%) and amount of
dye adsorbed, qe (mg/g), for varying pH.

The results are highlighted in the given table

Table 18. Effect of solution pH on the photocatalytic degradation of RR with 20%TiO2@ZIF-

8/PANI.

pH Dye removal efficiency (%) Amount of dye adsorbed, qe (mg/g)

2 99.53 198.89
 3 99.12 197.98

5 99.24 198.5

6 97.25 193.01

7 80.96 167.68

9 51.67 113.91

10 54.75 122.38

The nanocomposite displayed better RR removal performance at slightly acidic condition, 99.24%
removal and qe 198.5 at pH 5 (which is the initial pH of the dye solution), and this performance
remained better even at extreme acidic solutions, 99.12% removal and qe 197.98 at pH 3 and
99.53% removal and qe 198.89 at pH 2. When the pH of the solution goes toward the neutral
medium from pH 5, the performance starts to decrease as at pH 6 the removal efficiency is 97.25%
and qe 193.01. However, at neutral pH the removal efficiency drastically reduces to 80.96% and
qe value turns to 167.68. Conversely, in the basic side removal efficiency initially reduced in a
sharp pace upto pH 9, which demonstrates 51.67% removal, and then sharply maintained to
54.75% removal at pH 10, with a qe value of 122.38.

As aforementioned, the zero charge point is the point at which the surface charge of the
photocatalyst is zero (pHPZC). When the catalyst is at zero charge point (pHPZC), organic
contaminants are less drawn to it. At various pH the zeta potential of the 3D nanocomposite has
been measured and displayed in figure 4.8. Figure 4.8 demonstrates that (pHPZC) for 20%
TiO2@ZIF-8/PANI is 8.06. Therefore, at pH<pHPZC, protonation reaction takes place and the
catalyst surface is positively charged. On the other hand, the catalyst surface becomes negatively
charged when the deprotonation reaction happens at pH> pHPZC [Shuvo101].

So, when the value of pH lowers from 8.06 the surface charge of the catalyst is positive and as
demonstrated in the figure 4.8, the surface charge becomes very higher at pH less than 5. From the
above figure, it was seen that the percent degradation of dyes was maximum at pH 2. As RR is an
anionic dye, in the aqueous solution it contains negative charges-

(Dye-SO3H) -------→ (Dye-SO3-) + H+

As a result of the opposing charge, facilitation of an electrostatic connection between the catalyst
and the RR dye molecule. Conversely, with increasing basicity of the medium, deprotonation of
funtionalized linkers occurred causing initial decline in performance [E85][86] The drastic change
in dye removal efficiency at pH 9 can be attributed to zero charge point. Hence it can be stated that
at pH 9, the surface of synthesized nanocomposite became negatively charged and so it repelled
the anionic dye causing negligible adsorption through electrostatic force of attraction.

4.2.2.2. Effect of initial dye concentration:

It is important from the mechanistic as well as application point of view to study the dependence
of the dye removal efficiency on the initial dye concentration. Generally, dye removal rate
increases with the increase in initial dye concentration to a certain level and a further increase in
dye concentration leads to decrease in dye removal rate. Similar results were found in this study
and it is summarized in following figure 4.x and table.

Experimental condition

Initial RR concentration: 10−60 mg/L

Volume of RR solution: 50 mL

Catalyst amount: 5 mg

Natural pH: 5.34

Sunlight Irradiation: 60 minutes

Figure 4.20: Study of the effect of initial dye concentration on RR removal performance of
20%TiO2@ZIF-8/PANI at pH 5.34 with 0.2g/L dosage of adsorbent, dye removal efficiency (%)
as well as amount of dye removed qe, (mg/g).

Table 19. Effect of initial dye concentration on the photocatalytic degradation of RR with
20%TiO2@ZIF-8/PANI.

Initial RR Dye removal efficiency Amount of dye adsorbed, qe (mg/g)

concentration (ppm) (%)

10 98.78 98.78

20 99.24 198.48

30 95.81 287.43

40 85.24 340.96

50 73.21 366.05

60 64.11 384.66
In this experiment, the extent of dye removal efficiency initially increased upto 20 ppm
concentration of initial dye concentration, and then gradually decreased with further increase in
concentration. It can be assumed that in case of 20 ppm dye solution, adsorption equilibrium
reached and so removal efficiency could not increase for dye solutions of higher concentration.
Yet the dye removal performance remained moderate even at initial dye concentration of 30 ppm,
and 40 ppm with 95.81%, and 85.24% removal efficiency, respectively.

Apart from adsorption, photocatalysis played a vital role here for dye removal and photocatalytic
performance, in general, degrades with rise in initial concentration. Since sunlight irradiation is
evenly distributed among analyte and dye particles during photocatalysis, the higher concentration
of dye particles causes limited extent of irradiation left for analytes. Thus, electron excitation to
conduction band reduces due to lack of sufficient energy and so electron-hole pair generation
efficiency drops to certain extent. Furthermore, concentrated dye solutions produce a passivation
layer so that sunlight could not penetrate it to reach the catalysts in significant extent. This general
scenario found to occur in our experiment causing decrease in dye removal efficiency with
increasing initial dye concentration. However, this reduction in efficiency can be minimized by
strictly controlling other operating parameters.

The dye concentration in industrial textile effluents vary greatly on the basis of effluent collection
point and final effluent can be treated by the synthesized nanocomposite in multiple stages to
overcome the reduction in degradation efficiency.

4.2.2.3. Effect of irradiation time:

The amount of time during which the synthesized compounds were allowed to be in proper contact
with dye solutions is considered here as irradiation time. It is a crucial parameter for adsorption
and photocatalysis experiments because kinetics as well as mechanism of such processes entirely
depends upon the contact period. In this study, the effect of time on dye removal performance of
synthesized nanocomposites, were investigated where initial dye solution was optimized at 20 ppm
and operating pH was maintained at 5.34 with an adsorbent dosage rate of 5mg. The experiment
was conducted for one hour under direct sunlight and nearly 2 mL solution from the system was
withdrawn in every 15 minutes for comparison study. The result of this experiment is shown in
following figure 4.x, and table.
Experimental condition

Initial RR concentration: 20 mg/L

Volume of RR solution: 50 mL

Photocatalyst amount: 5 mg

Natural pH: 5.34

Sunlight irradiation: 15-60 minutes

Figure 4.21. Effect of contact time on the RR removal efficiency (%) of all synthesized
nanocomposites (ZIF-8, PANI, TiO2, ZIF-8/PANI, and 20%TiO2@ZIF-8/PANI), at optimized
operating condition.
Table 20. Effect of irradiation time on the photocatalytic degradation of RR removal efficiency
(%) with ZIF-8, PANI, TiO2, ZIF-8/PANI, 20%TiO2@ZIF-8/PANI.

Time Removal Removal Removal Removal Removal

(min) efficiency (%) efficiency (%) efficiency (%) efficiency (%) efficiency (%)
by ZIF-8 by PANI by TiO2 by ZIF- by 20%
8/PANI TiO2@ZIF-
8/PANI

15 29.25 14.76 54.23 32.88 71.87

30 47.11 25.11 69.11 56.24 89.25

45 57.31 31.23 75.19 70.17 96.33

60 59.82 34.55 77.43 74.45 99.24

As shown in the figure 4.x, nearly 72% removal occurred for our synthesized 20% TiO2@ZIF-
8/PANI composite at the very beginning of the experiment, 15 minutes, and more than 89%
removal was obtained after half an hour. Then removal rate became slower with 96.33% dye
removal for 45 minutes and later 99.24% in one hour. This trend is somehow similar with the usual
adsorption data where initial removal rate is too rapid and that of final stage is too slow.

The initial rate of dye removal was fast because surface adsorption occurred at this stage to greater
extent. Highly porous structure of synthesized nanocomposite, 20% TiO2@ZIF-8/PANI, provided
enormous number of active sites for adsorption. Besides, the molecular size of RR is large enough
to get trapped within framework’s cavities. At the same time photocatalysis of dye solution
occurred, generating photo-active radicals. Since both processes simultaneously took place, initial
degradation or removal rate was significant.

After first 15 minutes, dye removal rate was also noticeable and probable reason can be diffusion
of dye within framework structure until it gets trapped. The step of diffusion was comparatively
slower than surface adsorption and so removal rate somehow reduced, while photocatalysis
occurred at the same pace as initial stage. Finally, when further diffusion was not possible because
of entrapment, photocatalysis assumed to be sole responsible for dye removal. This is why dye
removal rate reduced further and ended with 99.24% removal efficiency.

4.2.2.4. Effect of % of TiO2 in the ternary composite:

The % of TiO2 has a significant role in the photocatalytic activity of the ternary 3D nanocomposite.
To optimize the % of TiO2, three composites have been synthesized as aforementioned, taking
10%, 20%, and 30% weight TiO2 in comparison to ZIF-8/PANI composite.

For comparison, the RR removal performances of synthesized 3D nanocomposites varying with

different wt% TiO2 were carried out in the same conditions provided below,

Experimental condition

Initial RR concentration: 20 mg/L

Volume of RR solution: 50 mL

Catalyst amount: 5 mg

Natural pH: 5.34

Sunlight Irradiation: 60 minutes

The result of this experiment is shown in following figure 4.x, and table.

Table 21. Effect wt% of TiO2 on the composite on the photocatalytic degradation of RR removal
efficiency (%)

wt% TiO2 in composite Dye removal efficiency (%) Amount of dye adsorbed, qe
(mg/g)

10% TiO2@ZIF-8/PANI 93.81% 189.93

20% TiO2@ZIF-8/PANI 99.24% 198.11

30% TiO2@ZIF-8/PANI 90.74% 185.12

Figure 4.22: Effect of the % of TiO2 on the 3D nanocomposite to RR removal efficiency (%) as
well as amount of dye adsorbed, qe (mg/g), where 10%, 20%, and 30% TiO2 denotes the
10%TiO2@ZIF-8/PANI, 20%TiO2@ZIF-8/PANI, and 30%TiO2@ZIF-8/PANI, respectively.

Interestingly, it was observed that efficiency of 3D nanocomposites increased with increasing

quantity of TiO2 up to a precise value (20wt%) and then decreased (30wt%). The RR removal rates
(irradiation time 60 mins and pH 5.34) were in the following order: 30%TiO2@ZIF-8/PANI
(90.74%) < 20%TiO2@ZIF-8/PANI (99.24%) > 10%TiO2@ZIF-8/PANI (93.81%). Compared
with other nanocomposites, 20%TiO2@ZIF-8/PANI showed enhanced efficiency on account of
two main reasons. Firstly, from the UV-VIS DRS data it has been seen that the band gap energy
(3.13 eV) for 20%TiO2@ZIF-8/PANI is higher than, (3.21 eV) 10%TiO2@ZIF-8/PANI
photocatalyst. However, the case is not for 30%TiO2@ZIF-8/PANI which exhibits even minimum
band gap energy (3.08 eV) then 20%TiO2@ZIF-8/PANI. Nonetheless, it still falls short as a
significant amount of rutile phase conversion occurs in case of 30%TiO2@ZIF-8/PANI as
aforementioned in XRD characterization for which the electron hole pair recombines hugely (as
shown in the PL characterization). That’s why the optimized amount of TiO2 is 20 wt%.

4.2.3. Control experiments:

In previous section, the role of adsorption and photocatalysis were assumed considering the effect
of contact time. Yet, the contribution of both processes towards dye removal was investigated by
conducting distinct experiments either at dark or under sunlight irradiation for one hour at
optimized operating condition (pH 5.34, initial dye concentration: 20 ppm, adsorbent or catalyst
dosage: 5mg). The results of control experiments are clearly illustrated in figure 4.x.

Figure 4.23: Comparison of the removal of RR dye by synthesized 20%TiO2@ZIF-8/PANI

nanocomposite in sunlight and dark. where, (a) Absorbance spectra showing dye solutions before
and after conducting control experiments, (b) RR dye removal efficiency considering either
adsorption or photocatalysis, as well as their synergistic effect.
It is clear from figure 4.x. (b) that respectively 99.24% and 61.33% dye removal efficiencies were
obtained with and without sunlight. So, the subtraction of either values, i.e. 37.91% dye removal
was due to photocatalysis and the 61.33% dye removal occurred by adsorption. In figure (a), the
red bar indicates dye removal efficiency by adsorption whereas the light green bar indicates that
by synergistic effect of adsorption and photocatalysis.

Thus it is evident that adsorption played more crucial role compared to photocatalysis, mainly
because the synthesized nanocomposite had significant number of active sites and extremely
porous structure. Both surface adsorption and diffusion into the porous structure assumed to be
responsible for such enhanced adsorption. Ionic interaction and hydrogen bond formation were
vital for this process. On the other hand, photocatalysis played a comparative minor role in
synergy. Yet, it was not insignificant.

4.2.4. Mineralization of Remazol Red (RR):

The amount of carbon linked to organic substances can be estimated using total organic carbon
analysis (TOC). Total organic carbon was measured in order to evaluate the mineralization of RR.
This might be used to measure the extent to which RR molecules are degraded during adsorption
and photocatalysis. Higher TOC removal values indicate that the organic contaminants have been
fully mineralized, which is preferred during photocatalysis to reduce the production of potentially
harmful byproducts [S86].

Experimental condition

Initial RR concentration: 20 mg/L

Volume of RR solution: 50 mL

Catalyst amount: 5 mg

pH: 5.34

Sun light irradiation: 0-90 mins

Figure 4.24. Schematic illustration demonstrating the mineralization of RR during the adsorption
and photodegradation with synthesized 20%TiO2@ZIF-8/PANI.

Table 22. TOC Values of initial and treated RR solutions under sunlight using 20%TiO2@ZIF-
8/PANI. (initial TOC = 9.82 ppm)

Time (min) TOC reduction of RR (%) TOC (ppm)

15 53.66 4.55

30 76.06 2.35

45 82.99 1.67

60 86.35 1.34

75 88.60 1.11
 90 89.30 1.05

The TOC removal values make it clear that after the 60 mins irradiation, a small amount of organic
degradation byproducts remained in solution. The mineralization of RR was observed at about
86.35% after 1 hour of solar iraadiation. Mineralization of RR was reported to be 89.30% after 90
minutes by solar irradiation. It implies that smaller byproducts of the breakdown of the organic
molecules were produced before the mineralization of CO2, H2O, and other inorganic species. For
complete mineralization of these residual organic materials, prolonged irradiation times may be
necessary [S103].

4.2.5. Role of radical scavenger:

In order to understand the potential contribution from various active species towards the
degradation of RR, radicle trapping experiments were carried out. In this experiment ammonium
oxalate (AO), ascorbic acid (AA) and 2-propanol (2P) were introduced as scavenger for holes,
superoxide and hydroxyl radicle respectively. For comparison purpose, a separate experiment
without scavenger (WS) and additional experiment for calculating photolysis of RR under sunlight
were conducted separately.

Experimental condition

Initial RR concentration: 20 mg/L

Volume of RR solution: 50 mL

Catalyst amount: 5 mg

pH: 5.34

Sun light irradiation: 60 mins

The result of radicle trapping experiment is schematically depicted in figure 4.x.

Figure 4.25. Schematic representation of radicle trapping experiments for RR removal by
20%TiO2@ZIF-8/PANI. (a) Absorbance spectra of respective experiments, (b) Comparison of %
removal of RR dye in each experiment.

These particular scavengers were selected based on the fact that for photo degradation of organic
pollutants, holes, superoxide and hydroxyl radicles play crucial role under visible light irradiation
[84]. As shown in figure 4.x., 99.24% removal of RR was found in the absence of any scavenger,
while 87.88% removal was obtained with ammonium oxalate, 79.39% with ascorbic acid, and
82.23% with 2-Propanol respectively. Since the removal efficiency is quiet similar in experiments
with each scavenger, all active radicles including holes, superoxide and hydroxyl radicles were
almost equally significant in photocatalytic degradation process. Thus oxidative degradation
occurred in all plausible pathways described in later section.

From the figure, it can also be displayed that, photolysis occurs almost 10% for this RR dye without
providing any catalyst.

Table 23. Effect of radical scavengers on the photocatalytic degradation of RR with under natural
sunlight irradiation for 1 hour by 20%TiO2@ZIF-8/PANI.
 Radical scavenger Reactive species Removal efficiency (%)

No scavenger --- 99.24

Ascorbic acid (AA) Superoxide radical ion (•O2–) 79.39

Di–ammonium oxalate Photogenerated holes (h+) 87.89

monohydrate (AO)

2-propanol Hydroxyl radical (•OH) 82.23

Photolysis -- 9.21

4.2.6. Photocatalyst reusability:

One of the most crucial properties of a material for removing pollutants from industrial effluents,
along with efficiency, is its ability to be recycled. When the material is appropriate for long-term
repeated applications, significant cost reduction is possible. The regeneration of the material after
each cycle should be simple. The pollutant removal technology becomes economical and feasible
with such reusable material.

Experimental condition

Initial RR concentration: 20 mg/L

Volume of RR solution: 50 mL

Catalyst amount: 5 mg

pH: 5.34

Sun light irradiation: 60 mins

The rate of degradation was calculated and photocatalyst was separated, washed carefully with
distilled water, and also by simple alkali (0.01 M NaOH) washing [Tabassum paper 58], so that
we can get the pH of 8.06 where the surface charge is 0 and dried at 70°C for 12hrs. The
photocatalyst was applied for the second cycle and introduced into new dye solution and the
photodegradation reaction was conducted under optimum conditions. The degradation experiment
was repeated for five cycles and at the end of each cycle, the rate of degradation was registered.
Figure 4.x. showed that the degradation rate of RR by our synthesized 20%TiO2@ZIF-8/PANI 3D
nanocomposite.

Figure 4.26. Demonstration of reusability of the 20%TiO2@ZIF-8/PANI 3D nanocomposite for

removing RR up to five cycles.

From the figure, efficiency decreased slightly through the first three cycles i.e., reached 93.87%
but gradual decrease was observed from cycle 4 to cycle 5 to be 89.4% and 77.55% respectively.
These results confirmed efficient recyclability of the synthesized composite for RR degradation
under sunlight.
From this experiment, it can be said that the nanocomposite is suitable for long-term repeated use
for the removal of similar toxic organic pollutants from the aqueous environment. Nearly complete
and very fast removal of anionic dye with long-term reusability makes this 3D nanocomposite a
promising candidate for industrial applications.

4.2.7. Adsorption isotherm analysis:

The distribution of adsorbate molecules on the adsorbent’s surface is determined by analyzing the
experimental results with isotherm models such as Langmuir, and Freundlich isotherms as these
equilibrium adsorption isotherms provide information about the homogeneity and heterogeneity
of the adsorbent surface. In present study following isotherm are used to be fitted with the
experimental information available.

4.2.7.1. Langmuir Adsorption Isotherm:

The Langmuir adsorption is valid for monolayer adsorption onto a surface containing a finite
number of identical sites. The model assumes uniform energies of adsorption onto the surface and
no transmigration of adsorbate in the plane of the surface. Langmuir adsorption parameters were
determined by transforming the Langmuir equation into linear form.

𝐶𝑒 𝐶𝑒 1
= +
𝑞𝑒 𝑞𝑚𝑎𝑥 𝑞𝑚𝑎𝑥 𝐾𝐿

Where, qe (mg/g) denotes the quantity of solute adsorbed in milligram at per gram substance of
the adsorbent at equilibrium; Ce (mg/L) is symbolized for equilibrium concentration of solute in
the solution and qmax (mg/g) represents the highest value of solute that could get adsorbed.

The Langmuir plot of all the synthesized materials are provided for RR,
Figure 4.27. The Langmuir adsorption isotherm plots for RR dye adsorption by synthesized
frameworks.

The Langmuir model was tested by plotting Ce/qe versus Ce as shown in the figure 4.x. The figure
represents Langmuir plots for synthesized frameworks (ZIF-8, PANI, ZIF-8/PANI, 20%TiO2@,
ZIF-8/PANI). As, the 20%TiO2@, ZIF-8/PANI cannot be seen properly, for a better visualization
it has been zoomed and showed in the upper graph. There was a linear relation between Ce/qe and
Ce at the room temperature in each case. The values of KL and qmax were calculated from the slope
and intercept of the Langmuir plot of Ce/qe versus Ce.

The theoretical maximum sorption capacity (qmax), which is the maximum amount of adsorbate
adsorbed per unit mass of adsorbent (mg/g), is calculated from the slope of the linear fit. The
maximum adsorption capacity was found to be 166.944 mg/g, 97.087 mg/g, 217.864 mg/g, and
204.4989 mg/g respectively for synthesized ZIF-8, PANI, ZIF-8/PANI, 20%TiO2@ZIF-8/PANI.
The predicted qmax values are in good agreement with the experimentally measured qe.
The essential features of the Langmuir isotherm may be expressed in terms of equilibrium
parameter RL, which is a dimensionless constant referred to as separation factor or equilibrium
parameter. The equation of RL is shown below.

1
𝑅𝐿 =
𝐾𝐿 + 𝐶𝑚

Where, Cm is the maximum initial dye concentration used in the adsorption experiments. RL gives
a qualitative measure of the favorability of the adsorption process; RL greater than 1 indicates
unfavorable adsorption and RL between 0 and 1 indicates a favorable process. In our study, RL
value was assessed to be 0.3739 L/mg, 0.3155 L/mg, 0.2375 L/mg, and 0.0756 L/mg for samples
with respective order mentioned earlier, regardless of the adsorption temperature. This suggests
very favorable adsorption processes for RR adsorption.

4.2.7.2. Freundlich Isotherm

This isotherm is commonly used to describe the adsorption characteristics for the heterogeneous
surface. The linearize form of equation is shown below.

1
𝑙𝑜𝑔𝑞𝑒 = 𝑙𝑜𝑔𝐾𝐹 + 𝑙𝑜𝑔𝐶𝑒
𝑛

The constant KF is an approximate indicator of adsorption capacity while 1/n is a function of the
strength of adsorption in the adsorption process. The graphs of log (Ce) vs log (qe) for adsorption
of RR dye by synthesized samples (ZIF-8, PANI, ZIF-8/PANI, 20%TiO2@ZIF-8/PANI) are
shown below.

Plotting log Ce vs log qe, both the values of KF and 1/n can be calculated from slope and intercept.
As n decreases, the adsorption becomes more difficult. For good adsorption n = 2–10, difficult
adsorption n = 1–2, and for poor adsorption n < 1.
Figure 4.28. The Freundlich adsorption isotherm plots for RR dye adsorption by synthesized
compounds.

In our study, value of n was found to be 2.112, 2.654, 2.0357, and 4.5783 for synthesisized ZIF-8,
PANI, ZIF-8/PANI, and 20%TiO2@ZIF-8/PANI respectively at the room temperature. This
indicates that the process of adsorption was favorable in all cases. Therefore, the outcome is
absolutely right from theoretical and experimental perspective. However, the maximum amount
of dye removed by these compounds was related to KF values and these values were not compatible
with experimental outcome.The KF values of synthesisized ZIF-8, PANI, ZIF-8/PANI, and
20%TiO2@ZIF-8/PANI are 31.36, 22.73, 60.380, and 274.814, respectively.

4.2.7.3. Discussion on Isotherm for RR

This section will provide a brief comparison between Langmuir adsorption model, and Freundlich
adsorption model for RR adsorption. This comparative study is summarized in table
Table 24. Discussion on isotherm for RR

Adsorption Parameters ZIF-8 PANI ZIF- 20%TiO2@ZIF-

isotherm 8/PANI 8/PANI

Langmuir isotherm qmax (mg/g) 166.944 97.087 217.864 204.4989

Langmuir isotherm qe (mg/g) 131.02 82.9 157.2 198.5

Langmuir isotherm KL (L/mg) 0.3739 0.3155 0.2375 0.0756

Langmuir isotherm R2 0.99368 0.97641 0.93047 0.99281

Freundlich isotherm KF 31.36 22.73 60.380 274.814

Freundlich isotherm n 2.112 2.654 2.0357 4.5783

Freundlich isotherm R2 0.9767 0.8071 0.98287 0.94363

The experimental values of qe for RR adsorption by synthesized compounds were pretty close to
that obtained assuming Langmuir adsorption isotherm. Thus it can be concluded that the
adsorption processes neither followed a non-uniform multilayer adsorption, described by
Freundlich model, but they could be accurately described by a Langmuir-type uniform monolayer
adsorption.

4.2.8. Kinetics of RR dye removal

Kinetics of reactions including chemisorption and photocatalysis provides essential information

involving insight into the reaction rate, value of rate constant, reaction mechanism as well as the
sorption mechanism and others. The most common kinetic models utilized to monitor and control
the reaction kinetics are Lagergren’s pseudo 1st order model and Ho’s pseudo 2nd order model. In
this study, both of these kinetic models were investigated to determine the kinetics of RR dye
removal by synthesized 3D nanocomposite as well as by other synthesized samples.

4.2.8.1. Lagergren pseudo 1st order kinetic model:

The Lagergren pseudo 1st order kinetic model is based on the assumption that the rate of change
of solute uptake; rate of dye removal in our study; is directly proportional to difference in saturation
concentration in and the amount of solid uptake with time, which is generally applicable to the
initial stage of an adsorption or other reactions. It is commonly observer that kinetics follows this
Lagergren pseudo 1st order equation when adsorption occurs through diffusion through the
interface.

The Lagergren pseudo 1st order model can be described by the linear form as follows.

ln(𝑞𝑒 − 𝑞𝑡 ) = 𝑙𝑛𝑞𝑒 − 𝐾1 𝑡

Where, qe (mg/g) and qt (mg/g) are the quantity adsorbed at equilibrium and at time t, respectively;
k1 (L/min) is the equilibrium rate constant in the pseudo 1st order model.

If an adsorption process follows true first order kinetics, then the intercept of ln(qe-qt) versus t
plots would be equal to ln of experimentally determined qe or adjusted to fit the experimental value.

In this study a plot of ln(qe-qt) versus t was drawn for the removal of RR dye by the synthesized
nanocomposites. The graphical sketch of this plot along with fitted kinetic equation of R2 value is
depicted in figure 4.x. The values of qe and k1 were calculated from the intercept and slope of this
plot using following equations.

𝑞e = exp (𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡)

𝑘1 = -𝑠𝑙𝑜𝑝𝑒
Figure 4.29. Investigation of pseudo 1st order kinetic model for RR dye removal.

Linear plots with negative slope were identified in each case. The assessed values for qe, k1 and R2
were 209.137 mg/g, 0.08197 L/min and 0.99362 respectively regarding dye removal by
20%TiO2@ZIF-8/PANI. The qe values for synthesized samples; ZIF-8, PANI, and ZIF-8/PANI;
were 211.156 mg/g, 187.939 mg/g, and 210.0026 mg/g respectively, while respective k1 values
were found to be 0.07782 L/min, 0.08998 L/min, and 0.0614 L/min.

4.2.8.2. Pseudo 2nd order kinetic model:

The pseudo 2nd order kinetic model is based on the assumption that the rate limiting step is
chemical reaction to form an intermediate complex during the progression of reaction and predicts
the behavior over whole range of reaction time. In this condition, the reaction rate is dependent on
catalytic capacity, not on concentration of catalyst. The equation for the pseudo 2nd order kinetic
model is given by,
 𝑡 1 𝑡
= +
𝑞𝑡 𝐾2 𝑞𝑒 2 𝑞𝑒
Where, qe is the amount of dye adsorbed at equilibrium (mg/g), k2 is the equilibrium rate constant
of pseudo 2nd order model (g/mg.min) and t represents time (min). The plot of t/qt as a function of
time should give a linear relationship between the quantity of dye removed and passage of time.

In this study, respective plots of t/qt versus time for removal of RR dye by the synthesized
nanocomposite and other samples were drawn and presented in figure 4.x.

Figure 4.30. Investigation of pseudo 2nd order kinetic model for RR dye removal.

The value of qe and k2 were determined from the slope and intercept respectively using

following equations.

𝑞e = 1 / slope

K2 = 1/ (intercept)* (𝑞e)2
Linear plots with positive slopes were identified in each case. The assessed values for qe, k2 and
R2 were 208.08 mg/g, 0.0005837 g/mg.min and 0.99955 respectively regarding dye removal by
20%TiO2@ZIF-8/PANI. The qe values for synthesized samples; ZIF-8, PANI, and ZIF-8/PANI;
were 173.010 mg/g, 86.1 mg/g, and 175.1313 mg/g respectively, while respective k1 values were
found to be 0.000236 g/mg.min, 0.000472 g/mg.min, and 0.000421 g/mg.min.

4.2.8.3. Discussion on kinetics investigation:

In previous sections, the kinetics of the removal of an anionic dye, Remazol Red, was modeled in
accordance with pseudo 1st order kinetics as well as pseudo 2nd order kinetics. Now this section
will provide a comparative analysis of both models on the basis of respective kinetic parameters
considering theoretical and experimental perspective. For better and convenient understanding, all
the data is presented in table x.

It is clear from the kinetic analysis that the value of equation parameter, R2, is pretty close to unity
in each analysis constituting both kinetic models. So, these plots were comprised of well fitted
equations. The experimental values for maximum quantity of dye removed or degraded by
individual samples at optimum operating condition with 20 ppm initial concentration dye solutions
were 131.02 mg/g, 82.9 mg/g, 157.2 mg/g, and 198.5 mg/g in respective order mentioned in table
x. These data are very similar with that determined assuming pseudo 2nd order kinetic model with
deviations less than 10 mg/g.

Therefore, it is needless to say that each synthesized compounds; ZIF-8, PANI, ZIF-8/PANI,
20%TiO2@ZIF-8/PANI; followed the pseudo 2nd order kinetic model for photocatalytic
degradation of anionic dye Remazol red.

Table 25. Summarized result of kinetics study for the removal of Remazol Red.

Kinetic model Parameters ZIF-8 PANI ZIF-8/PANI 20%TiO2@ZIF-

8/PANI

Pseudo 1st qcal (mg/g) 131.02 82.9 157.2 198.5

order
 Pseudo 1st qexp (mg/g) 211.156 187.939 210.002 209.137
order

Pseudo 1st K1(L/min-1) 0.07782 0.08998 0.0614 0.08197

order

Pseudo 1st R2 0.98408 0.99176 0.99974 0.99362

order

Pseudo 2nd K2(g/mg.min) 0.000236 0.000472 0.000421 0.0005837

order

Pseudo 2nd qexp (mg/g) 173.010 86.1 175.1313 208.08

order

Pseudo 2nd R2 0.98808 0.99373 0.99891 0.99955

order

4.3. Adsorption & photocatalytic performance study – Cationic dye

In order to study the adsorption and photocatalytic performance of the synthesized 3D

nanocomposite (TiO2@ZIF-8/PANI) towards cationic dye removal, auramine O (AO) was chosen.
This dye has cationic functional group that exhibits positively charged characteristics in aqueous
solution. A number of parameters, namely pH, time, and initial dye concentration were considered
while carrying out the study. The result of these batch experiments are briefly described in
following sections.

Initially the application was carried out at normal condition with all the synthesized photocatalysts
to compare their degradation efficiency. Later the photocatalysts with highest degradation
efficiency were optimized and used for the application on the degradation of the anionic dye at
various conditions aforementioned.

4.3.1. Performance of individual species:

Whether the performance of our synthesized composite (TiO2@ZIF-8/PANI) overshadowed that
of its constituent species can only be identified by comparison study of all samples (ZIF-8, PANI,
TiO2, ZIF-8/PANI, TiO2@ ZIF-8/PANI), without interrupting the operating parameters. During
this experiment, 20 ppm dye solution was considered as standard in room temperature with a
catalyst dosage rate of 0.2g/L, which means 5mg catalyst. The results are summarized in figure
5.x, utilizing the initial pH of AO dye which was found to be 6.11. The peak intensity reduces due
to the photocatalytic removal of AO dye in presence of photocatalysts and sunlight irradiation.
Experimental data are provided in Table X.

Experimental condition

Initial concentration: 20 mg/L;

Volume of AO solution: 50 mL;

Photocatalyst amount: 5 mg;

pH: 9.

Irradiation time: 60 minutes (Sunlight);

Figure 4.31: Comparative study of the performance of constituent species of synthesized
composites (ZIF-8, PANI, ZIF-8/PANI, TiO2, 20%TiO2@ZIF-8/PANI) towards AO dye removal.
(a) Absorbance spectra of dye solution before and after sunlight irradiation, (b) Dye removal
efficiency (%) and amount of dye removed, qe (mg/g), for individual samples.

As illustrated in above two figures, the synthesized nanocomposite, 20%TiO2@ZIF-8/PANI

demonstrated highest dye removal efficiency, 93.4% & qe value 187.6 mg/g in, only one hour. So,
it can be assumed that both polymerization of aniline and photo-active TiO2 incorporation into the
pristine ZIF-8 contributed towards better dye removal performance. Still, the contribution by TiO2
is higher because it exhibited better efficiency and qe value (81.38%, and 169.5) than ZIF-8
(62.06%, and 132.10), PANI (26.20%, and 60.6), as well as ZIF-8/PANI (72.13%, and 154.1). The
reasons for the improved visible light harvesting property leads to enhance photocatalytic activities
of 20%TiO2@ZIF-8/PANI are,

• Decreased bandgap energy due to incorporation of TiO2

• Increased adsorption rate through H-bonds due to polymerization of aniline into ZIF-8.
• Reduced photoinduced electron/ hole recombination rate as aforementioned in
PL(Shuvo[68], [86], [87].

Table 26. Adsorption and photocatalytic removal for AO dye under sunlight irradiation by the
synthesized materials

Synthesized Material Removal efficiency (%) qe (mg/g)

ZIF-8 62.06% 132.10

PANI 26.20% 60.6

ZIF-8/PANI 72.10% 154.1

TiO2 81.96% 169.5

20%TiO2@ZIF-8/PANI 93.4% 187.5

Thus the synthesized nanocomposite, 20%TiO2@ZIF-8/PANI was optimized through this study
and further investigations were carried out in following sections.

4.3.2. Effect of different parameters on removal of AO dye:

Removal of dyes or any other pollutants from aqueous solution by any substrate is strongly
controlled by a number of experimental parameters. Some parameters strongly affect the removal
process while some parameters play minor role. To identify the maximum efficiency of a material
for pollutant removal, it is suggested to work with a good number of experimental parameters and
find out the optimum value of each parameter. Among different parameters influencing the dye
removal capacity of our composite, the following important parameters were focused on:

1. pH
2. % of TiO2 in the ternary composite
3. Initial concentration of AO dye
4. Irradiation time
4.3.2.1. Effect of pH:

The pH of the reaction mixture can have a significant impact on the rate of adsorption and
photocatalytic activity of the catalyst. This is because the size and surface properties of aggregated
nanoparticles are controlled by the pH. Finally, it controls the concentration of reactive hydroxyl
radicals. It can also affect the charge of organic pollutants.

Experimental condition

Initial dye concentration: 20 mg/L

Volume of AO solution: 50 mL

Catalyst amount: 5 mg

pH: 2−10

Sunlight irradiation: 60 min

The concentration of hydrogen ion in aqueous solution is crucial for ionic interaction. Since the
anionic dye removal principle is based on ionic interactions and H-bonds formation with
adsorbent, pH is a significant parameter in this study. Therefore, AO removal experiments using
the synthesized 3D nanocomposite (20%TiO2@ZIF-8/PANI) were performed with a wide range
of pH variation from 2 to 10. The summarized result of these trials is demonstrated in following
figure and table.

Figure 4.32: Study of the effect of pH on AO dye removal performance of 20%TiO2@ZIF-8/PANI

in 20 ppm dye solution with 0.2g/L dosage of adsorbent (a) Absorbance spectra of dye solution
before and after sunlight irradiation for one hour, (b) Dye removal efficiency (%) and amount of
dye adsorbed, qe (mg/g), for varying pH.

The results are highlighted in the given table

Table 27. Effect of solution pH on the photocatalytic degradation of RR with 20%TiO2@ZIF-

8/PANI.

pH Dye removal efficiency (%) Amount of dye adsorbed, qe (mg/g)

2 31.6 72.31
 3 29.8 69.09

5 36.53 85.135

6 51.67 112.85

7 71.12 150.91

9 93.42 187.5

10 89.91 182.12

The nanocomposite displayed better AO removal performance at slightly alkaline condition,

93.4% removal and qe 187.01 at pH 9 attained by adding some 0.1N NaOH solution, and this
performance decreased even at extreme basic solutions, 89.91% removal and qe 182.12 at pH 10.
When the pH of the solution goes toward the neutral medium from pH 9, the performance starts to
decrease as at pH 7 the removal efficiency is 71.12% and qe 150.91. However, at lower pH the
removal efficiency drastically reduces to 51.67% and qe value turns to 112.85. Conversely, in the
acidic medium, obtained by adding 0.1N HCl, removal efficiency initially reduced in a sharp pace
upto pH 3, which demonstrates 29.80% removal, and then slightly increased to 31.6% removal at
pH 2, with a qe value of 72.31.

As aforementioned, the zero charge point is the point at which the surface charge of the
photocatalyst is zero (pHPZC). When the catalyst is at zero charge point (pHPZC), organic
contaminants are less drawn to it. At various pH the zeta potential of the 3D nanocomposite has
been measured and displayed in figure 4.8. Figure 4.8 demonstrates that (pHPZC) for 20%
TiO2@ZIF-8/PANI is 8.06. Therefore, at pH<pHPZC, protonation reaction takes place and the
catalyst surface is positively charged. On the other hand, the catalyst surface becomes negatively
charged when the deprotonation reaction happens at pH> pHPZC [Shuvo101].

So, when the value of pH lowers from 8.06 the surface charge of the catalyst is positive and as
demonstrated in the figure 4.8, the surface charge becomes very higher at pH less than 5. From the
above figure, it was seen that the percent degradation of dyes was minimum at pH 3. As AO is an
cationic dye, in the aqueous solution it contains positive charges-
 (Dye-NH2) -------→ (Dye-NH3+) + Cl-

As a result of the similar charge, the surface of the catalyst and the surface of dye result in repulsion
and less amount of dye molecule is adsorbed. With increasing the pH value of the solution the
positive surface charge decreases and the removal efficiency starts to increase. After pHv 8.06 the
surface charge of the catalyst turns negative. Which results in the facilitation of an electrostatic
connection between the catalyst and the AO dye molecule. The maximum resultant negative
charge is obtained for pH 9.0 (as shown in the Zeta potential characterization). As a result,
maximum removal efficiency occurs at that pH. After that, increasing that pH to 10 results in
decreasing dye removal efficiency as the negative charge intensity decreases. Hence it can be
stated that at pH 9, the surface of synthesized nanocomposite became negatively charged and so it
attracted the cationic dye causing maximum adsorption through electrostatic force of attraction, as
well as maximum removal rate.

4.3.2.2. Effect of initial dye concentration:

It is important from the mechanistic as well as application point of view to study the dependence
of the dye removal efficiency on the initial dye concentration. Generally, dye removal rate
increases with the increase in initial dye concentration to a certain level and a further increase in
dye concentration leads to decrease in dye removal rate. Similar results were found in this study
and it is summarized in following figure 4.x and table.

Experimental condition

Initial AO concentration: 10−60 mg/L

Volume of AO solution: 50 mL

Catalyst amount: 5 mg

pH: 9.00

Sunlight Irradiation: 60 minutes

Figure 4.33: Study of the effect of initial dye concentration on AO removal performance of
20%TiO2@ZIF-8/PANI at pH 9 with 0.2g/L dosage of adsorbent, dye removal efficiency (%) as
well as amount of dye removed qe, (mg/g).

Table 28. Effect of initial dye concentration on the photocatalytic degradation of RR with
20%TiO2@ZIF-8/PANI.

Initial Dye removal Amount of dye adsorbed, qe (mg/g)

AOconcentration efficiency (%)
(ppm)

10 92.89 92.88

20 93.42 186.84

30 91.07 273.21
 40 85.23 340.92

50 73.43 367.15

60 61.18 368.58

In this experiment, the extent of dye removal efficiency initially increased upto 20 ppm
concentration of initial dye concentration, and then gradually decreased with further increase in
concentration. It can be assumed that in case of 20 ppm dye solution, adsorption equilibrium
reached and so removal efficiency could not increase for dye solutions of higher concentration.
Yet the dye removal performance remained moderate even at initial dye concentration of 30 ppm,
and 40 ppm with 91.07%, and 85.23% removal efficiency, respectively.

Apart from adsorption, photocatalysis played a vital role here for dye removal and photocatalytic
performance, in general, degrades with rise in initial concentration. Since sunlight irradiation is
evenly distributed among analyte and dye particles during photocatalysis, the higher concentration
of dye particles causes limited extent of irradiation left for analytes. Thus, electron excitation to
conduction band reduces due to lack of sufficient energy and so electron-hole pair generation
efficiency drops to certain extent. Furthermore, concentrated dye solutions produce a passivation
layer so that sunlight could not penetrate it to reach the catalysts in significant extent. This general
scenario found to occur in our experiment causing decrease in dye removal efficiency with
increasing initial dye concentration. However, this reduction in efficiency can be minimized by
strictly controlling other operating parameters.

The dye concentration in industrial textile effluents vary greatly on the basis of effluent collection
point and final effluent can be treated by the synthesized nanocomposite in multiple stages to
overcome the reduction in degradation efficiency.

4.3.2.3. Effect of irradiation time:

The amount of time during which the synthesized compounds were allowed to be in proper contact
with dye solutions is considered here as irradiation time. It is a crucial parameter for adsorption
and photocatalysis experiments because kinetics as well as mechanism of such processes entirely
depends upon the contact period. In this study, the effect of time on dye removal performance of
synthesized nanocomposites, were investigated where initial dye solution was optimized at 20 ppm
AO solution and operating pH was maintained at 9 with an adsorbent dosage rate of 5mg. The
experiment was conducted for one hour under direct sunlight and nearly 2 mL solution from the
system was withdrawn in every 15 minutes for comparison study. The result of this experiment is
shown in following figure 4.x, and table.

Experimental condition

Initial AO concentration: 20 mg/L

Volume of AO solution: 50 mL

Photocatalyst amount: 5 mg

pH: 9

Sunlight irradiation: 15-60 minutes

As shown in the figure 4.x, more than 69% removal occurred for our synthesized 20% TiO2@ZIF-
8/PANI composite at the very beginning of the experiment, 15 minutes, and almost 82% removal
was obtained after half an hour. Then removal rate became slower with 89.34% dye removal for
45 minutes and later 93.4% in one hour. This trend is somehow similar with the usual adsorption
data where initial removal rate is too rapid and that of final stage is too slow.
Figure 4.34. Effect of contact time on the AO removal efficiency (%) of all synthesized
nanocomposites (ZIF-8, PANI, TiO2, ZIF-8/PANI, and 20%TiO2@ZIF-8/PANI), at optimized
operating condition.

Table 29. Effect of irradiation time on the photocatalytic degradation of AO removal efficiency
(%) with ZIF-8, PANI, TiO2, ZIF-8/PANI, 20%TiO2@ZIF-8/PANI.

Time Removal Removal Removal Removal Removal efficiency

(min) efficiency efficiency efficiency efficiency (%) (%) by 20%
(%) by ZIF-8 (%) by PANI (%) by TiO2 by ZIF-8/PANI TiO2@ZIF-8/PANI

15 31.37 13.56 59.6 46.98 69.22

30 49.62 19.13 71.22 59.15 81.99

45 57.84 24.08 78.29 67.34 89.34

60 61.95 26.23 81.78 72.11 93.42

The initial rate of dye removal was fast because surface adsorption occurred at this stage to greater
extent. Highly porous structure of synthesized nanocomposite, 20% TiO2@ZIF-8/PANI, provided
enormous number of active sites for adsorption. Besides, the molecular size of AO is large enough
to get trapped within framework’s cavities. At the same time photocatalysis of dye solution
occurred, generating photo-active radicals. Since both processes simultaneously took place, initial
degradation or removal rate was significant.

After first 15 minutes, dye removal rate was also noticeable and probable reason can be diffusion
of dye within framework structure until it gets trapped. The step of diffusion was comparatively
slower than surface adsorption and so removal rate somehow reduced, while photocatalysis
occurred at the same pace as initial stage. Finally, when further diffusion was not possible because
of entrapment, photocatalysis assumed to be sole responsible for dye removal. This is why dye
removal rate reduced further and ended with 93.4% removal efficiency. Besides, both ionic and
non-ionic interactions between dye molecule and analyte compounds came to the point of
saturation after a certain time period. This phenomenon could also be held responsible for decrease
in dye removal rate with time.

4.3.2.4. Effect of % of TiO2 in the ternary composite:

The % of TiO2 has a significant role in the photocatalytic activity of the ternary 3D nanocomposite.
To optimize the % of TiO2, three composites have been synthesized as aforementioned, taking
10%, 20%, and 30% weight TiO2 in comparison to ZIF-8/PANI composite.

For comparison, the AO removal performances of synthesized 3D nanocomposites varying with

different wt% TiO2 were carried out in the same conditions provided below,

Experimental condition

Initial AO concentration: 20 mg/L

Volume of AO solution: 50 mL

Catalyst amount: 5 mg

pH: 9.00

Sunlight Irradiation: 60 minutes

The result of this experiment is shown in following figure 4.x, and table.

Table 30. Effect wt% of TiO2 on the composite on the photocatalytic degradation of AO removal
efficiency (%)

wt% TiO2 in composite Dye removal efficiency (%) Amount of dye adsorbed, qe
(mg/g)

10% TiO2@ZIF-8/PANI 83.28% 169.56

20% TiO2@ZIF-8/PANI 93.42% 187.84

30% TiO2@ZIF-8/PANI 76.37% 157.74

Figure 4.35. Effect of the % of TiO2 on the nanocomposite to AO removal efficiency (%) as well
as amount of dye adsorbed, qe (mg/g), where 10%, 20%, and 30% TiO2 denotes the
10%TiO2@ZIF-8/PANI, 20%TiO2@ZIF-8/PANI, and 30%TiO2@ZIF-8/PANI, respectively.

Interestingly, it was observed that efficiency of 3D nanocomposites increased with increasing

quantity of TiO2 up to a precise value (20wt%) and then decreased (30wt%). The RR removal rates
(irradiation time 60 mins and pH 9.0) were in the following order: 30%TiO2@ZIF-8/PANI
(76.67%) < 20%TiO2@ZIF-8/PANI (93.42%) > 10%TiO2@ZIF-8/PANI (83.28%). Compared
with other nanocomposites, 20%TiO2@ZIF-8/PANI showed enhanced efficiency on account of
two main reasons. Firstly, from the UV-VIS DRS data it has been seen that the band gap energy
(3.13 eV) for 20%TiO2@ZIF-8/PANI is higher than, (3.21 eV) 10%TiO2@ZIF-8/PANI
photocatalyst. However, the case is not for 30%TiO2@ZIF-8/PANI which exhibits even minimum
band gap energy (3.08 eV) then 20%TiO2@ZIF-8/PANI. Nonetheless, it still falls short as a
significant amount of rutile phase conversion occurs in case of 30%TiO2@ZIF-8/PANI as
aforementioned in XRD characterization for which the electron hole pair recombines hugely (as
shown in the PL characterization). That’s why the optimized amount of TiO2 is 20 wt%.

Besides, there is another interesting thing to notice. In comparison to the anionic dye removal %,
the performance of the cationic dye removal % exhibits a drastic decrease. This may be on account
of the fact that, photocatalysis is dominant for this case, and wt% TiO2 played a more crucial role.

4.3.3. Control experiments:

In previous section, the role of adsorption and photocatalysis were assumed considering the effect
of contact time. Yet, the contribution of both processes towards dye removal was investigated by
conducting distinct experiments either at dark or under sunlight irradiation for one hour at
optimized operating condition (pH 9, initial dye concentration: 20 ppm, adsorbent or catalyst
dosage: 5mg). The results of control experiments are clearly illustrated in figure 4.x.
Figure 4.36. – Comparison of the removal of AO dye by synthesized 20%TiO2@ZIF-8/PANI
nanocomposite in sunlight and dark. where, (a) Absorbance spectra showing dye solutions before
and after conducting control experiments, (b) AO dye removal efficiency considering either
adsorption or photocatalysis, as well as their synergistic effect.

It is clear from figure 4.x. (b) that respectively 93.42% and 31.01% dye removal efficiencies were
obtained with and without sunlight. So, the subtraction of either values, i.e. 62.41% dye removal
was due to photocatalysis and the 31.01% dye removal occurred by adsorption. In figure (a), the
red bar indicates dye removal efficiency by adsorption whereas the light green bar indicates that
by synergistic effect of adsorption and photocatalysis.

The synthesized nanocomposite (20%TiO2@ZIF-8/PANI) proved to be an excellent photocatalyst

for degrading auramine O dye, yet adsorptive properties were not significant. The reason behind
poor adsorption is molecular size of dye mismatched with the porous structure of the composite
framework. The molecular size of auramine O is comparatively smaller and so it could not get
trapped within framework cavity, instead passed through the composite. Only adsorption at the
surface was possible due to electrostatic interactions between oppositely charged compounds in
alkaline aqueous solution, and hydrogen bonding can also occur. This can be a plausible
explanation of outcome of control experiments.
 4.3.4. Mineralization of Auramine O dye:

The amount of carbon linked to organic substances can be estimated using total organic carbon
analysis (TOC). Total organic carbon was measured in order to evaluate the mineralization of AO.
This might be used to measure the extent to which AO molecules are degraded during adsorption
and photocatalysis. Higher TOC removal values indicate that the organic contaminants have been
fully mineralized, which is preferred during photocatalysis to reduce the production of potentially
harmful byproducts.

Experimental condition

Initial AO concentration: 20 mg/L

Volume of AO solution: 50 mL

Catalyst amount: 5 mg

pH: 9

Sun light irradiation: 0-90 mins

Figure 4.37. Schematic illustration demonstrating the mineralization of AO dye during the
adsorption and photodegradation with synthesized 20%TiO2@ZIF-8/PANI.
Table 31. TOC Values of initial and treated AO solutions under sunlight using 20%TiO2@ZIF-
8/PANI. (initial TOC = 7.98 ppm)

Time (min) TOC reduction of AO (%) TOC (ppm)

15 23.80 6.08

30 41.47 4.67

45 56.01 3.51

60 66.79 2.65

75 74.81 2.01

90 80.07 1.59

The TOC removal values make it clear that after the 60 mins irradiation, a small amount of organic
degradation byproducts remained in solution. The mineralization of AO was observed at about
66.79% after 1 hour of solar iraadiation. Mineralization of AO was reported to be 80.07% after 90
minutes by solar irradiation. It implies that smaller byproducts of the breakdown of the organic
molecules were produced before the mineralization of CO2, H2O, and other inorganic species. For
complete mineralization of these residual organic materials, prolonged irradiation times may be
necessary [S103].

4.3.5. Role of radical scavenger:

In order to understand the potential contribution from various active species towards the
degradation of RR, radicle trapping experiments were carried out. In this experiment ammonium
oxalate (AO), ascorbic acid (AA) and 2-propanol (2P) were introduced as scavenger for holes,
superoxide and hydroxyl radicle respectively. For comparison purpose, a separate experiment
without scavenger (WS) and additional experiment for calculating photolysis of AO under sunlight
were conducted separately.

Experimental condition
Initial AO concentration: 20 mg/L

Volume of AO solution: 50 mL

Catalyst amount: 5 mg

pH: 9.0

Sun light irradiation: 60 mins

The result of radicle trapping experiment is schematically depicted in figure 4.x.

Figure 4.38. Schematic representation of radicle trapping experiments for AO removal by

20%TiO2@ZIF-8/PANI. (a) Absorbance spectra of respective experiments, (b) Comparison of %
removal of AO dye in each experiment.

These particular scavengers were selected based on the fact that for photo degradation of organic
pollutants, holes, superoxide and hydroxyl radicles play crucial role under visible light irradiation
[E84]. As shown in figure 4.x., 93.42% removal of AO was found in the absence of any scavenger,
while 63.44% removal was obtained with ammonium oxalate, 46.19% with ascorbic acid, and
71.9% with 2-Propanol respectively. Since the removal efficiency is not quite similar in
experiments with each scavenger.
Additional experiments regarding photolysis of AO dye under direct sunlight without any catalyst
were conducted. Nearly 11.47% photolysis of AO dye without any catalyst was obtained.

These results indicated that superoxide radical ion (•O2–), showed a significant and predominated
effect in the degradation process both under sunlight [Fahim4]. The photogenerated holes (h+) also
played an important role in the photocatalytic degradation of AO. Finally, in the case of sunlight
degradartion of AO, hydroxyl radical (•OH) has the least effect on the degradation process of AO.

Table 32. Effect of radical scavengers on the photocatalytic degradation of AO with under natural
sunlight irradiation for 1 hour by 20%TiO2@ZIF-8/PANI.

Radical scavenger Reactive species Removal efficiency (%)

No scavenger --- 93.42

Ascorbic acid (AA) Superoxide radical ion (•O2–) 46.19

Di–ammonium oxalate Photogenerated holes (h+) 63.44

monohydrate (AO)

2-propanol Hydroxyl radical (•OH) 71.90

Photolysis -- 11.47

4.3.6. Photocatalyst reusability:

One of the most crucial properties of a material for removing pollutants from industrial effluents,
along with efficiency, is its ability to be recycled. When the material is appropriate for long-term
repeated applications, significant cost reduction is possible. The regeneration of the material after
each cycle should be simple. The pollutant removal technology becomes economical and feasible
with such reusable material.
Experimental condition

Initial AO concentration: 20 mg/L

Volume of AO solution: 50 mL

Catalyst amount: 5 mg

pH: 9.0

Sun light irradiation: 60 mins

The rate of degradation was calculated and photocatalyst was separated, washed carefully with
distilled water, and also by simple acid (0.01 M HCl) washing [Tabassum paper 58], so that we
can get the pH of 8.06 where the surface charge is 0 and dried at 70°C for 12hrs. The photocatalyst
was applied for the second cycle and introduced into new dye solution and the photodegradation
reaction was conducted under optimum conditions. The degradation experiment was repeated for
five cycles and at the end of each cycle, the rate of degradation was registered. Figure 4.x. showed
that the degradation rate of AO by our synthesized 20%TiO2@ZIF-8/PANI 3D nanocomposite.

Figure 4.39. Demonstration of reusability of the 20%TiO2@ZIF-8/PANI 3D nanocomposite for

removing AO up to five cycles.
From the figure, efficiency decreased slightly through the first three cycles i.e., reached 89.37%
but gradual decrease was observed from cycle 4 to cycle 5 to be 83.01% and 71.33% respectively.
These results confirmed efficient recyclability of the synthesized composite for AO degradation
under sunlight.

From this experiment, it can be said that the nanocomposite is suitable for long-term repeated use
for the removal of similar toxic organic pollutants from the aqueous environment. Nearly complete
removal of cationic dye with long-term reusability makes this 3D nanocomposite a promising
candidate for industrial applications.

4.3.7. Adsorption isotherm analysis:

The distribution of adsorbate molecules on the adsorbent’s surface is determined by analyzing the
experimental results with isotherm models such as Langmuir, and Freundlich isotherms as these
equilibrium adsorption isotherms provide information about the homogeneity and heterogeneity
of the adsorbent surface. In present study following isotherm are used to be fitted with the
experimental information available.

4.3.7.1. Langmuir Adsorption Isotherm:

The Langmuir adsorption is valid for monolayer adsorption onto a surface containing a finite
number of identical sites. The model assumes uniform energies of adsorption onto the surface and
no transmigration of adsorbate in the plane of the surface. Langmuir adsorption parameters were
determined by transforming the Langmuir equation into linear form.

𝐶𝑒 𝐶𝑒 1
= +
𝑞𝑒 𝑞𝑚𝑎𝑥 𝑞𝑚𝑎𝑥 𝐾𝐿

Where, qe (mg/g) denotes the quantity of solute adsorbed in milligram at per gram substance of
the adsorbent at equilibrium; Ce (mg/L) is symbolized for equilibrium concentration of solute in
the solution and qmax (mg/g) represents the highest value of solute that could get adsorbed.

The Langmuir plot of all the synthesized materials are provided for AO,
Figure 4.40. The Langmuir adsorption isotherm plots for AO dye adsorption by synthesized
frameworks.

The Langmuir model was tested by plotting Ce/qe versus Ce as shown in the figure 4.x. The figure
represents Langmuir plots for synthesized frameworks (ZIF-8, PANI, ZIF-8/PANI, 20%TiO2@,
ZIF-8/PANI). As, the 20%TiO2@, ZIF-8/PANI cannot be seen properly, for a better visualization
it has been zoomed and showed in the upper graph. There was a linear relation between Ce/qe and
Ce at the room temperature in each case. The values of KL and qmax were calculated from the slope
and intercept of the Langmuir plot of Ce/qe versus Ce.

The theoretical maximum sorption capacity (qmax), which is the maximum amount of adsorbate
adsorbed per unit mass of adsorbent (mg/g), is calculated from the slope of the linear fit. The
maximum adsorption capacity was found to be 165.28 mg/g, 89.84 mg/g, 175.50 mg/g, and 191.38
mg/g respectively for synthesized ZIF-8, PANI, ZIF-8/PANI, 20%TiO2@ZIF-8/PANI. The
predicted qmax values are in good agreement with the experimentally measured qe.
The essential features of the Langmuir isotherm may be expressed in terms of equilibrium
parameter RL, which is a dimensionless constant referred to as separation factor or equilibrium
parameter. The equation of RL is shown below.

1
𝑅𝐿 =
𝐾𝐿 + 𝐶𝑚

Where, Cm is the maximum initial dye concentration used in the adsorption experiments. RL gives
a qualitative measure of the favorability of the adsorption process; RL greater than 1 indicates
unfavorable adsorption and RL between 0 and 1 indicates a favorable process. In our study, RL
value was assessed to be 0.049 L/mg, 0.041 L/mg, 0.038 L/mg, and 0.006921 L/mg for samples
with respective order mentioned earlier, regardless of the adsorption temperature. This suggests
very favorable adsorption processes for AO adsorption.

And the values of KL are 0.1384, 0.09899, 0.2, and 0.8228 for synthesized ZIF-8, PANI, ZIF-
8/PANI, 20%TiO2@ZIF-8/PANI.

4.3.7.2. Freundlich Isotherm

This isotherm is commonly used to describe the adsorption characteristics for the heterogeneous
surface. The linearize form of equation is shown below.

1
𝑙𝑜𝑔𝑞𝑒 = 𝑙𝑜𝑔𝐾𝐹 + 𝑙𝑜𝑔𝐶𝑒
𝑛

The constant KF is an approximate indicator of adsorption capacity while 1/n is a function of the
strength of adsorption in the adsorption process. The graphs of log (Ce) vs log (qe) for adsorption
of AO dye by synthesized samples (ZIF-8, PANI, ZIF-8/PANI, 20%TiO2@ZIF-8/PANI) are
shown below.

Plotting log Ce vs log qe, both the values of KF and 1/n can be calculated from slope and intercept.
As n decreases, the adsorption becomes more difficult. For good adsorption n = 2–10, difficult
adsorption n = 1–2, and for poor adsorption n < 1.
Figure 4.41. The Freundlich adsorption isotherm plots for AO dye adsorption by synthesized
compounds.

In our study, value of n was found to be 2.01, 3.03628, 2.2243, and 2.06778 for synthesisized ZIF-
8, PANI, ZIF-8/PANI, and 20%TiO2@ZIF-8/PANI respectively at the room temperature. This
indicates that the process of adsorption was favorable in all cases. Therefore, the outcome is
absolutely right from theoretical and experimental perspective. However, the maximum amount
of dye removed by these compounds was related to KF values and these values were not compatible
with experimental outcome.The KF values of synthesisized ZIF-8, PANI, ZIF-8/PANI, and
20%TiO2@ZIF-8/PANI are 33.86, 21.36, 44.07, and 125.27, respectively.

4.3.7.3. Discussion on Isotherm for AO

This section will provide a brief comparison between Langmuir adsorption model, Freundlich
adsorption model, and Temkin adsorption model for AO adsorption. This comparative study is
summarized in table
Table 33. Discussion on isotherm for AO dye

Adsorption Parameters ZIF-8 PANI ZIF- 20%TiO2@ZIF-

isotherm 8/PANI 8/PANI

Langmuir isotherm qmax (mg/g) 165.28 89.84 175.50 191.38

Langmuir isotherm qe (mg/g) 132.10 60.60 154.1 187.5

Langmuir isotherm KL (L/mg) 0.1384 0.09899 0.200 0.8228

Langmuir isotherm R2 0.98041 0.97358 0.98156 0.99018

Freundlich isotherm KF 31.36 22.73 60.380 274.814

Freundlich isotherm N 2.01 3.03628 2.2243 2.06778

Freundlich isotherm R2 0.97308 0.98346 0.99304 0.97491

The experimental values of qe for AO adsorption by synthesized compounds were pretty close to
that obtained assuming Langmuir adsorption isotherm. Thus it can be concluded that the
adsorption processes neither followed a non-uniform multilayer adsorption, described by
Freundlich model, nor temkin, but they could be accurately described by a Langmuir-type uniform
monolayer adsorption.

4.3.7. Kinetics of AO dye removal

Kinetics of reactions including chemisorption and photocatalysis provides essential information

involving insight into the reaction rate, value of rate constant, reaction mechanism as well as the
sorption mechanism and others. The most common kinetic models utilized to monitor and control
the reaction kinetics are Lagergren’s pseudo 1st order model and Ho’s pseudo 2nd order model. In
this study, both of these kinetic models were investigated to determine the kinetics of AO dye
removal by synthesized 3D nanocomposite as well as by other synthesized samples.

4.2.9.1. Lagergren pseudo 1st order kinetic model:

The Lagergren pseudo 1st order kinetic model is based on the assumption that the rate of change
of solute uptake; rate of dye removal in our study; is directly proportional to difference in saturation
concentration in and the amount of solid uptake with time, which is generally applicable to the
initial stage of an adsorption or other reactions. It is commonly observer that kinetics follows this
Lagergren pseudo 1st order equation when adsorption occurs through diffusion through the
interface.

The Lagergren pseudo 1st order model can be described by the linear form as follows.

ln(𝑞𝑒 − 𝑞𝑡 ) = 𝑙𝑛𝑞𝑒 − 𝐾1 𝑡

Where, qe (mg/g) and qt (mg/g) are the quantity adsorbed at equilibrium and at time t, respectively;
k1 (L/min) is the equilibrium rate constant in the pseudo 1st order model.

If an adsorption process follows true first order kinetics, then the intercept of ln(qe-qt) versus t
plots would be equal to ln of experimentally determined qe or adjusted to fit the experimental value.

In this study a plot of ln(qe-qt) versus t was drawn for the removal of AO dye by the synthesized
nanocomposites. The graphical sketch of this plot along with fitted kinetic equation of R2 value is
depicted in figure 4.x. The values of qe and k1 were calculated from the intercept and slope of this
plot using following equations.

𝑞e = exp (𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡)

𝑘1 = -𝑠𝑙𝑜𝑝𝑒
Figure 4.42. Investigation of pseudo 1st order kinetic model for AO dye removal.

Linear plots with negative slope were identified in each case. The assessed values for qe, k1 and R2
were 153.496 mg/g, 0.07297 L/min and 0.99372 respectively regarding AO dye removal by
20%TiO2@ZIF-8/PANI. The qe values for synthesized samples; ZIF-8, PANI, and ZIF-8/PANI;
were 227.81866 mg/g, 90.81 mg/g, and 204.84 mg/g respectively, while respective k1 values were
found to be 0.08051 L/min, 0.07016 L/min, and 0.07587 L/min.

4.3.9.2. Pseudo 2nd order kinetic model:

The pseudo 2nd order kinetic model is based on the assumption that the rate limiting step is
chemical reaction to form an intermediate complex during the progression of reaction and predicts
the behavior over whole range of reaction time. In this condition, the reaction rate is dependent on
catalytic capacity, not on concentration of catalyst. The equation for the pseudo 2nd order kinetic
model is given by,
 𝑡 1 𝑡
= +
𝑞𝑡 𝐾2 𝑞𝑒 2 𝑞𝑒
Where, qe is the amount of dye adsorbed at equilibrium (mg/g), k2 is the equilibrium rate constant
of pseudo 2nd order model (g/mg.min) and t represents time (min). The plot of t/qt as a function of
time should give a linear relationship between the quantity of dye removed and passage of time.

In this study, respective plots of t/qt versus time for removal of AO dye by the synthesized
nanocomposite and other samples were drawn and presented in figure 4.x.

Figure 4.43. Investigation of pseudo 2nd order kinetic model for AO dye removal.

The value of qe and k2 were determined from the slope and intercept respectively using

following equations.

𝑞e = 1 / slope

K2 = 1/ (intercept)* (𝑞e)2
Linear plots with positive slopes were identified in each case. The assessed values for qe, k2 and
R2 were 194.5525 mg/g, 0.000729 g/mg.min and 0.99911 respectively regarding dye removal by
20%TiO2@ZIF-8/PANI. The qe values for synthesized samples; ZIF-8, PANI, and ZIF-8/PANI;
were 179.533 mg/g, 128.86 mg/g, and 236.966 mg/g respectively, while respective k1 values were
found to be 0.000193 g/mg.min, 0.0001559 g/mg.min, and 0.0001932 g/mg.min.

4.3.9.3. Discussion on kinetics investigation:

In previous sections, the kinetics of the removal of a cationic dye, Auramine O, was modeled in
accordance with pseudo 1st order kinetics as well as pseudo 2nd order kinetics. Now this section
will provide a comparative analysis of both models on the basis of respective kinetic parameters
considering theoretical and experimental perspective. For better and convenient understanding, all
the data is presented in table x.

It is clear from the kinetic analysis that the value of equation parameter, R2, is pretty close to unity
in each analysis constituting both kinetic models. So, these plots were comprised of well fitted
equations. The experimental values for maximum quantity of dye removed or degraded by
individual samples at optimum operating condition with 20 ppm initial concentration dye solutions
were 132.1 mg/g, 60.6 mg/g, 154.1 mg/g, and 187.5 mg/g in respective order mentioned in table
x. These data are very similar with that determined assuming pseudo 2nd order kinetic model with
deviations very less.

Therefore, it is needless to say that each synthesized compounds; our desired 20%TiO2@ZIF-
8/PANI; followed the pseudo 2nd order kinetic model for photocatalytic degradation of cationic
dye Auramine O.

Table 34: Summarized result of kinetics study for the removal of AO.

Kinetic Parameters ZIF-8 PANI ZIF-8/PANI 20%TiO2@ZIF-

model 8/PANI

Pseudo 1st qcal (mg/g) 132.10 60.6 154.10 187.5

order
 Pseudo 1st qexp (mg/g) 227.81866 90.81 204.84 153.496
order

Pseudo 1st K1(L/min-1) 0.08051 0.07016 0.07587 0.07297

order

Pseudo 1st R2 0.98691 0.97232 0.94954 0.99372

order

Pseudo 2nd K2(g/mg.min) 0.000193 0.0001559 0.0001932 0.000729

order

Pseudo 2nd qexp (mg/g) 179.533 128.86 236.966 194.5525

order

Pseudo 2nd R2 0.97688 0.92794 0.95926 0.99911

order

Table 35: Comparison of the significant photocatalytic degradation characteristics of RR and AO

dye.

Photocatalysts Dye and Photocatalys Time Light Removal Reference

conc. t (min source Efficienc
Loading ) y
(%)
TS0.75CS0.25 Remazol 5mg 90 Sunligh 95.7 [mitu apu]
red dye, t
10 ppm
Carbon-Modified Remazol 50mg 180 Visible 100 [Angewante
Titanium Dioxide red dye, light chemie]
20 ppm
PVDF/NiFe2O4/G Remazol 10 mg 100 UV-C 92.38 [Developing a
O red dye, robust
20ppm photocatalytic
and antifouling
performance of
PVDF
membrane
using spinel
 NiFe2O4/GO
photocatalyst
for efficient
industrial dye
wastewater
treatment]
20%TiO2@ZIF- Remazol 5mg 60 Visible 99.24 This study
8/PANI red dye, light
20 ppm
(PMMA)-based Auramin 2mg 90 Visible 65.4 [Trimetallic
Ag/ZnO/TiO2 e O dye, light composite
trimetallic 3 ppm nanofibers for
bifunctional antibacterial
nanofibers and
photocatalytic
dye degradation
of mixed dye
water]
Carbon–CaO Auramin 10mg 60 Visible 88.39 [Adsorption and
nanocomposites e O dye, light photocatalytic
20 ppm degradation of
auramine–O
dye using
carbon
nanoparticles
and Carbon–
CaO
nanocomposites
]
Graphitic carbon Auramin 10 mg 120 Visible 80.12% [Graphitic
nitride e O dye, light carbon nitride: a
10ppm sustainable
photocatalyst
for organic
pollutant
degradation and
antibacterial
applications]
20%TiO2@ZIF- Auramin 5 mg 60 Visible 93.40% This study
8/PANI e O dye, light
20 ppm

4.3.10. Mechanism Investigation of dye removal

The removal of RR and AO from aqueous solution by 20%TiO2@ZIF-8/PANI 3D nanocomposite
occurred in two distinct steps namely adsorption (for RR 61.33%, and for AO 31.01%) and
photocatalysis (for AO 62.41%, and for RR 37.91%). In this case, adsorption not only aided
photocatalysis but also effectively contributed in dye molecule removal. So, mechanisms of both
steps are being considered individually.

Adsorption:

Anionic azo dye, RR, got adsorbed on the protonated polyaniline in composite surface at optimum
condition (pH 5.34). The major interaction between them is electrostatic attraction between
oppositely charged moieties creating strong bonds via chemisorption [E87][88].

Z[-(C6H5-NH-C6H5NH)-]+ + R-SO3- → Z[-(C6H5-NH-C6H5NH)-]+ - O3S-R

Where, Z[-(C6H5-NH-C6H5NH)-]+, R-SO3-, and Z[-(C6H5-NH-C6H5NH)-]+ - O3S-R, represent

composite, anionic dye molecule (RR) and resultant chemisorbed species respectively.

Besides, multiple weak bonds such as hydrogen bonds, metal coordination and ℼ-ℼ conjugation
between aromatic rings can be held responsible for successful adsorption of dye molecules in
aqueous solution [E89] The plausible interactions between anionic dye molecule and synthesized
nanocomposite are illustrated in figure X.
Figure 44. The illustration of adsorption mechanism of RR by 20%TiO2@ZIF-8/PANI 3D
nanocomposite.

Photocatalysis:

Considering observations from control experiment, photocatalysis (attributed nearly 62.41%)

played the major role in the removal of auramine O from aqueous solution by the synthesized
nanocomposite (20%TiO2@ZIF-8/PANI). Conversely, adsorption (only 31.01%) was not
significant, despite being the preliminary step to provide proper contact between adsorbate and
adsorbent. The adsorption of dye molecule at the surface of nanocomposite as well as the
absorption of radiation both could be hold responsible for photocatalysis to occur. On the other
hand, photocatalysis (attributed nearly 37.91%) played the minor role in the removal of remazol
red from aqueous solution by the synthesized nanocomposite (20%TiO2@ZIF-8/PANI).
Conversely, adsorption (only 61.33%) was significant. The dye removal can be illustrated via the
mechanism shown in figure X. The process of photocatalysis of dyes can be simplified through
following steps.

• The absorption of ultraviolet and/or visible light from sun caused the promotion of
electrons from the valance band to conduction band leaving behind a positive hole in
valance band. As a result, photoactive electron (e-CB) and hole (h+VB) pairs were generated.

TiO2@ZIF-8/PANI + hv → h+VB + e-CB

Figure 45. Schematic representation of photocatalysis degradation mechanism of AO and RR by

20%TiO2@ZIF-8/PANI composite.
• The photo-generated conduction electron ionized oxygen to produce reactive superoxide
ions (•O2-) which further produced active species such as hydroxyl (•OH) and
hydroperoxyl (•OOH) radicles via following reactions [E83].

e-CB + O2 → •O2-

•O2-+ H2O → HOO• + OH-

•O2- + 2 e-CB + 2H+ → HO• + OH-

• The electro-negative species (OH-) previously generated was neutralized in this step by
simply combining with electro-positive holes. Besides, hole produced protons (H+) and
additional hydroxyl radicles in aqueous solution.
h+VB + OH-→ •OH
h+VB + H2O → •OH + H+
• Afterwards, hydrogen peroxide (H2O2) was formed and zero-valent oxygen was produced
as byproduct.
2(HOO•) → H2O2 + O2
• In this step, hydrogen peroxide immediately decomposed to produce active free radicals
causing the reduction of oxygen for the second time.
H2O2 + e-CB → HO- + •OH
• Finally, the adsorbed molecules of AO/RR were decomposed by successive oxidative
attack of active radicles.
•OH + AO/RR dye → degradation products
•O2- + AO/RR dye → degradation products
• Direct oxidation of dye molecules could also happen by reacting with holes.
h+VB + AO/RR dye → degradation products

The overall reaction can be summarized as,

h+VB/•OH + AO/RR dye → intermediates → CO2 + H2O
 Chapter 5. Conclusion

Conclusion

This study was aimed at facile synthesis of TiO2@ZIF-8/PANI 3D nanocomposite for

environmental remediation of wastewater. This purpose was smoothly executed during the entire
time period of research work. Pristine ZIF-8 was synthesized according to reported procedure, and
then interfacial polymerization to ensure better surface properties for adsorption compared to that
of parent ZIF-8. At the same time, TiO2 nanoparticle was incorporated in the framework and thus
final nanocomposite was produced. Successful synthesis was confirmed via characterization tools
namely XRD, FTIR, XPS, FESEM, UV-DRS, PL, DLS, Zeta potential and BET surface area
analysis. The adsorptive and photocatalytic performances were figure out by experimental analysis
of cationic and anionic dye removal from aqueous solution. This is the summarized scheme of this
research work and the outcome is highly promising. More than 99% degradation of anionic dye
was found in only one hour. Besides, more than 93% of cationic dye was found in only one hour.
In terms of future outlook, effect of temperature on dye removal could be investigated. Generally,
photocatalysts demonstrate better performance at temperatures a bit higher than room temperature
if they possess indirect band gaps. Since our nanocomposite also exhibited indirect band gaps as
well as sub band gaps, slightly higher temperature would surely reduce the time frame for ensuring
best catalytic performance. Hence, in upcoming time period effect of temperature and other
parameters might be checked for bringing this work to another level ahead. And finally, after
monitoring all parameters laboratory works could be repeated for larger scales.