1 s2.0 S2949839223000445 Main

Sustainable Chemistry for the Environment 4 (2023) 100044
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Sustainable Chemistry for the Environment

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Role of nanoparticles as oxidation catalyst in the treatment of textile

wastewater: Fundamentals and recent advances
Ramanan Mahadevan a, Shanmugam Palanisamy b, *, Prakadeeshraj Sakthivel b
a
Department of Chemical Engineering, Kongu Engineering College, Erode 638060, Tamil Nadu, India
b
Department of Food Technology, K.S.Rangasamy College of Technology, Tiruchengode, 637215 Namakkal, Tamil Nadu, India
A R T I C L E I N F O A B S T R A C T
Keywords: Dye (textile) wastewater constitutes of highly complex toxic substances including salts and organic compounds
Hydroxyl radicals that are to be separated and purified in secondary or tertiary treatment in order to provide reusable water. In this
Sulfate radicals context, oxidation processes are gaining attention in textile effluent treatment due to their high efficiency and
Oxidation
less harmful (CO2, H2O and Metal hydroxides or sulfates) by-products. AOPs (Advance Oxidation Processes) are
Nanoparticles
Dye
promoted and stabilized by the use of nanoparticles-based catalysts (metal oxides or carbonaceous nano
Waste water materials) with high surface area, stability and other beneficial relevant properties. The efficiency, reusability
and characteristics of various metal, metal oxides and carbonaceous catalytic materials in hydroxyl radical and
PDS (peroxydisulfate)/PMS (peroxymonosulfate) related oxidation processes of wastewater treatment are dis
cussed in this review. The related activation mechanisms of the hydroxyl and sulfate radicals have been also
elaborated, along with the effect of oxidation parameters, such as pH and pollutant concentration. The maximum
removal efficiency of organic pollutant can reach values of 96%, while applying the adsorptive bubble separation
method, can reach as high as 99% removal efficiency. This review describes the merits and demerits of un
supported and supported nanoparticles that are involved in AOPs. This study represents in selecting better
suitability of oxidation catalyst with good regenerability in various parameter like pH, pollutant concentration
and capacity.
1. Introduction Textile industry is a major water polluting industry around many

regions of the developing countries. Textile industries mainly consist of
Rapid industrialization and urbanization produce wastewater that colouring/dyeing process which adds colour to the fabrics using
makes the chance of direct source of pollutant into freshwater. Partic different fine chemicals and adsorbent. It involves dissolving synthetic
ularly, organic pollutants of this wastewater are growing concern to organic dyes and inorganic salts in potable water. This generates a
deplete fresh water sources day-to-day. The wastewater produced from wastewater of high colour, BOD, COD and lots of dissolved salts with
these industries can directly affect the water bodies and indirectly organic dye chemicals. After finished product is obtained in wet pro
pollute the soil and aquatic life. In recent decades, awareness of cessing operations, the ejected dyes and chemicals constitute the major
wastewater treatment techniques is necessary to process organic pol component of the produced wastewater [9]. High contaminant chem
lutants from by-products of petroleum refining, petrochemical, pesti icals and dyes containing acids, alkalis, and organic hydrocarbons with
cides, plastic, pharmaceutical, agrochemicals, paper and pulp, textile, heteroatom, starch, surfactants dispersing agents, soaps and metals with
tannery, food and chemical industries are intensively carried out [1,2]. toxicity may pollute the soil, sediment and surface water of the
Even at low concentrations, these contaminants in water bodies can ecosystem [10]. There are many challenges to overcome in the treat
cause considerable damage to life in the ecosystem, and reflect its ment and recycling of this wastewater for irrigation and reuse within the
impact directly on human health to a greater extent [3–8]. It is textile industries.
mandatory to ensure that the quality of the wastewater be well treated in There are different treatment techniques available in handling dye
environmental regulatory norms with degraded contaminants before effluent from textile industries including physical, biological, chemical
discharging into water bodies or reusing within the scope of the process. and their hybrid processes [10–13]. These technologies have been tested
* Corresponding author.
E-mail address: [email protected] (S. Palanisamy).
https://doi.org/10.1016/j.scenv.2023.100044
Received 10 March 2023; Received in revised form 29 September 2023; Accepted 8 October 2023
Available online 17 October 2023
2949-8392/© 2023 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
R. Mahadevan et al. Sustainable Chemistry for the Environment 4 (2023) 100044
and developed to treat wastewater efficiently and economically. eV which are non-selective. In addition, these radicals have high
There are two methods - physical and biological methods, used in oxidation potential to degrade the chemical compounds under ambient
wastewater treatment. The physical methods consists of the most conditions. Due the low production of radicals (depends on the oxidising
economical techniques namely adsorption, coagulation, flocculation agent concentration) compared to AOP, it has relatively low rate of
and filtration [12–14]. Irrespective of the properties and characteristics degradation.
of the organic or inorganic contents, adsorption has been widely prac AOPs are considered as a highly competitive technology which has
ticed by researchers to use a low cost adsorbent material to remove the gained attention for successfully removing or degrading recalcitrant
colour. But, the inefficient regeneration of adsorbents and heavy sludge pollutants by utilizing free radicals such as hydroxyl (•OH) or sulfate
generation might restrict the use of absorbents in bulk quantities and 4 ) radicals in aqueous medium [1–4]. In addition to the main
(SO•−
inevitably affecting the cost of adsorbent and the operation itself. In such treatment process, AOPs can be used for the pre-treatment of contami
case, even low-cost carbon adsorbent like peat, coal, fly ash, resins and nated water for the conventional or biological treatment. Toxic con
biotic resources like groundnut shell, date stones, potato plant, rice taminants and organic compounds in the wastewater can induce a
husk, ginger waste, wheat and corn straw residues can have disposal (or microbe membrane rupture or reduce survival rate of microorganism. So
dumping) issues or incineration problems [15,16]. Due to the difference AOPs can be used as effective pre-treatment method to remove toxic
in shape, size, charge and density of the suspended particles in the compounds for biological treatment processes [5,6]. It is noted that few
effluent, it can be removed and treated by coagulation and flocculation AOPs, such as ultrasonic, have high operating cost or produce undesired
technology. However, this technique for removal of colour, salt and by-products which limit its commercial scaling up in industries. There
metal can produce an enormous amount of the resultant sludge with an are many numbers of investigations in using ozone as oxidation agents in
expensive coagulant. Thus the process is limited due to low efficiency in presence or absence of catalyst [7,8]. The non-catalytic ozonation pro
the decolourisation. Similarly, filtration techniques, such as ultrafiltra cessing of textile dyes has high efficiency in alkaline pH with •OH
tion, nanofiltration and reverse osmosis, are used to recover and reuse radicals but performance of catalytic process such as CuS (400 mg/L for
water [17]. The wastewater content and temperature is very essential to treating textile dye containing waste water) in acidic pH shows better
know the filter and its permeability to have a proper selection of the degradation efficiencies [9].
membranes. The high cost of membranes, fouling and rejected water Heterogeneous catalytic oxidation processes have mainly attracted
streams are the main disadvantages in considering filtration technology the researcher due to their ease of recovering and reusing of the catalyst
to be adapted in industries [18–20]. with minimum quantity of material requirement [16–20]. This makes
Biological treatment can remove the dissolved organic matter in the the catalyst more cost effective and environmentally safer in removing
effluent in which the temperature, oxygen and microorganism load contaminants from the wastewater. The organic molecules to be elimi
respective to organic load implicate the effective removal efficiency nated and the chemical structure of the catalyst might specify the
[17]. It is classified into aerobic (presence of oxygen) and anaerobic catalyst quantity in the process. Low consumption oxidative agents and
(absence of oxygen) methods, in these processes the effluents undergo envisaging large-scale facility implements with high-performance cata
biological digestion with chemical hydrocarbons by producing meth lysts for achieving total degradation of organic contaminants are still in
anogenic biogas and organic sludge with salts. However, the resilient progress in the research field.
strains adapted by microorganisms to survive naturally in this method Literatures had reviewed some of the hybrid oxidation process in
can produce less quantity and hazardous sludge compared to the phys wastewater treatment such as H2O2/UV, UV/O3, ultrasound (US)/
ical methods. It is preferred for a particular type of chemical waste with hydrogen peroxide (H2O2) and US/O3 [10]. Further, there are only a few
potent microbe selection below the tolerance limit, but it isn’t suitable review articles in oxidation process that provide information on ho
for common effluent treatment processes and inorganic salt dissociation. mogenous and heterogeneous catalytic processes involved in the
The adaptability of the selected microbes and the enzyme activity in a wastewater treatment [11–14]. Later, highlight of the very recent ad
specific condition mainly influences the efficiency of biodegradation. vancements and prospects of catalytic AOPs in treating textile waste
Industries have long been commercially operational with the phys water and the disadvantages and solutions of the current conventional
ical and biological methods in most part of the wastewater treatments methods in removing organic pollutants are reported [15]. Though these
[20]. However, the industries have made effort to deal with the sludge reviews were made based on •OH radical mechanism, broad study in
generation and its toxic chemical effects which are produced from these effective degradation of textile effluent has been made using SO•− 4 rad
traditional treatment methods. To proceed without endangering human icals [10–18]. It is proved as SO•− 4 radical shows better performance
health and living organism, the processes are required to be more using nanoparticles in the oxidation process.
effective, lower cost and of robust nature to decontaminate and disinfect So, the progress of nanoparticles as heterogeneous oxidation cata
wastewater in developing and sub-developing countries [19,20]. lysts in COMs and AOPs of the textile dying effluent are important to
Currently, oxidation methods in the wastewater treatment are shown review regarding its present advancements and possible innovations in
more interest due to their high rate of organic pollutant decomposition treatment techniques [19,20]. In this review, we have highlighted the
and ease of the process methodology. Particularly, high interest is shown most recent advancements and prospects of heterogeneous catalysts,
in catalytic oxidation method by researchers because of the high effi unsupported and supported nanoparticles as oxidation catalysts and
ciency and effective handling of large volumetric flow rates with low summarize the performance & catalytic activity of the material in spe
sludge discharge. cific dye contaminant wastewater. In this article, the formation mech
Oxidation methods are most effective and easy to apply in removing anisms of •OH and SO•− 4 radicals in catalytic oxidation of AOP and their
chemical and part of inorganic salts. This method is categorized as application in wastewater treatment is presented. The chemical reaction
Chemical Oxidation Method (COM) and Advanced Oxidation Process in the treatment techniques is always complex and have high energy
(AOP). Under ambient condition, these processes proved to partially or requirement, the complex chemical reaction has to be studied widely
completely degrade the chemicals, dyes, carbohydrates, proteins, pes and have an broader understanding in existing system. The narrow
ticides and salts. Combining more than one technology together in the pathway of treating harmful organic compounds into harmless inorganic
treatment process is implied as hybrid technologies. Hybrid technologies compounds is main focus in present scenario to achieve the
have high scope and interest in pilot study for the commercial imple socio-economical treatment process. This review gives an overview and
mentation in the industries [1,2,5]. summary about the various existing reaction mechanism in the catalytic
COMs include the usage of oxidizing agents like H2O2 and ozone oxidation process. It is critical in identifying the most developed and
which facilitate the formation of strong reactive oxygen species (ROS) engineered treatment process that is eco-friendly and practically
like hydroxyl radicals (•OH) with high oxidation potential of about 2.8 possible in the oxidation processes. Therefore, in this review we provide
2
detailed information on dye degradation using nanoparticles for 4. Nanoparticles

oxidation of textile wastewater involving the use of •OH and SO•− 4
radicals. From this study, it will get benefit to identify the better treat Recent advancements and innovations in the synthesis of nano
ment mechanism and materials for environmental friendly application. materials in various shapes and sizes have drastically expanded the
range of applications of the materials in medicine, environmental sci
2. Perspective of AOPs ences, agriculture and food processing technology. In that case, Nano
materials have unique optical, magnetic, mechanical, electrical
From a conventional perspective, AOPs are interpreted as aqueous (electronic) and thermal properties [19–22]. Optical and electronic
phase oxidation methods where there is in-situ generation of highly properties in quantum size nanoparticles have colour characteristics
reactive radicals such as •OH or SO•−
4 , which are highly unstable and has with extent of different band of frequency in excitation band resulted on
huge oxidation potential, for the degradation of the target recalcitrant incident photon frequency to identify the variation based on colour.
contaminant. From a contemporary perspective, AOPs produce highly Also, free electron movements on the surface of these particles are easily
unstable and reactive radicals such as •OH and SO•− 4 radicals for the transportable in nanomaterials. Heterogeneous and homogenous catal
effectient removal of recalcitrant pollutant while avoiding the produc ysis, biomedicine, magnetic nanofluids and environment remediation
tion of a secondary effluent stream, through hybrid technologies based (water decontamination) are the major disciplines that magnetic prop
on the combination of various treatment processes with AOPs. These erties of nanomaterials are widely investigated. The maximum effi
combinations have major positive inflences on AOPs to avoid the ciency by using nanoparticles has shown on uneven electronic
prevalence of recalcitrant species and therefore enhancing the efficiency distribution material if the critical value of its size less than 10–20 nm.
of these overall process [21]. Elastic modulus, stress and strain, adhesion, hardness and friction on
A study by Dewil et al. [22] reviewed the effectivity of hybrid pro surface, engineering, nanofabrication and manufacturing are exten
cesses between AOPs and other processes including heterogeneous sively studied on nanoparticles for its application. Obviously, high
semiconductor photocatalysis, sulphate radical oxidation and electro thermal conductivity nanoparticles are widely investigated for nano
chemical advanced oxidation process for wastewater treatment. fluids, catalyst, colloids and various high temperature applications.
Nanoparticles provide astonishing catalytic activity due to its extremely
3. Catalytic oxidation in AOP small size and comparatively large surface area. Nanoparticles include
metal oxides, non-metals, metal atoms, composites and hybrid metal
In general, Oxidation can be carried out in two pathways, such as wet composites of various shapes providing unique catalytic properties.
air oxidation processes in which O2 is used for oxidation at different
conditions and use of high energy oxidants such as reactive oxygen in 5. Hydroxyl radicals
termediates like ozone and H2O2 and/or photons (•OH and SO•− 4 radi
cals). Catalyst in oxidation process can accelerate reaction rate towards In the last two decades, technologies have grown in the production of
chemical equilibrium by reducing activation energy of the degradation hydroxyl radical (•OH) for AOPs which received huge attention which
of organic compounds using oxidizing agents. The use of catalyst in any has been exponentially growing ever since in the research and devel
process must be selected based on completing a chemical process with opment of wastewater treatment technologies. Here, it may be used in
zero or minimal waste. This catalyst selection depends on selectivity, the successful degradation of recalcitrant and toxic (organic or inor
turnover frequency, stability and turnover number of that particular ganic) pollutants or may also be used as pre-treatment to convert
catalyst [16,17]. In oxidation process, catalysts are classified as ho recalcitrant pollutants into biodegradable compounds for conventional
mogenous and heterogeneous catalysts. The homogenous catalyst is the biological methods. The generation of the reactive oxygen radicals and
catalyst that exists in the same physical state as the reactant and uni residing period in the reactor chamber influence the efficiency of AOPs
formly dissolved or distributed in the reaction medium. Heterogeneous [23]. A detailed description of the hydroxyl radical formation mecha
catalyst exists in a different physical state from reactants such as nisms for few commercially viable nanomaterials in the AOPs is dis
liquid-solid, gas-solid or gas-liquid interfaces, where the reaction take cussed in this section. Summary of organic pollutants which were
place on the surface, external pores or internal ores of the catalyst ma removed by hydroxyl radical mechanism are presented in Table 1
terials. Some of the existing catalytic oxidation technologies are [27–48].
[11–26]:
5.1. Metal and metal oxide catalyst
• Fenton and Fenton-like Process
• Persulfate oxidation Process Numerous metal based-catalysts are used in the dye wastewater
• Catalytic cavitations Process (hydrodynamic and acoustic treatment by oxidation method. Particularly of mono-transition metals-
cavitations) based oxide such as Ti, Fe, Cu, Co, Mn, Au, Ag, Ce and Al are discussed in
• Sono-Chemical Process the literature [40–44]. Similarly, bimetallic catalysts are mostly proved
• Ozonation Process to be more efficient than monometallic due to synergy effect of selected
• Photolysis and Photo-oxidation (visible light and UV applications) metals in degradation mechanism. Degrading organic pollutant has
• Catalytic wet air oxidation successive nanoparticles as catalyst due to large surface area, small
• Photo-Electro chemical Process particle size, regenerability, high activity and stability. Though Fe-based
• Sono-Electro chemical Process catalyst are preferred in terms of cost, activity, toxicity, regeneration
• Electrochemical oxidation Process and earth abundance, but TiO2 is popular to attain maximum efficiency
in remediation of organic pollutant. Also, the metals are widely carried
Researchers show great potential of advancement in the use of with support materials like zeolite, SiO2, activated carbon, small organic
catalyst and their application in maximizing the efficiency of various molecules, polymers and membranes to avoid the passivation and
conventional AOPs. Though numerous catalysts have been recognized as agglomeration in cluster. Though the support has a significant role in the
potentially useful in waste management by oxidation process, but have catalytic activity, but the reactivity on pollutant degradation mostly
only focused on tertiary AOP treatment and pre-treatment process of dye depends on cost, surface contact, turn over frequency of active sites,
wastewater processing. performance and toxicity of nanoparticles [45–53].
3
Table 1
Catalytic process using nanoparticle as catalyst using oxidation process by hydroxyl radicals on dye effluent.
Assisted process Compounds Catalyst and Synthesis method Size Degradation mechanism Ref
oxidizing agents
Photocatalytic (UV) acenaphthylene ZnO/SiO2 Bioreduction method Particle size ranging Nanocatalyst loading = 1 g/L of [27]
from 8 ± 5 nm to 40 ± 5 ZnO/SiO2; temperature = 303 K;
nm, surface area= reaction time = 240 min;
150.25 m2/g percentage removal of COD(mg/l)
= 75%; percentage removal of
acenaphthylene = 73%.
Biological 4-nitrophenol, Pd with novel Schiff Simple surface 40 nm 100% conversion within a matter [28]
hexavalent chromium, base modified Unye modification of seconds for the mentioned
Rhodamine B, potassium bentonite pollutants; excellent stability ~ 4
hexacyanoferrate(III) months; excellent recyclability
and congo red. ~96% yield after seven
consecutive cycles.
Catalytic wet air Chlorophenolics CuO-CeO2 facile co-precipitation 3–10 nm for CeO2 and The highest removal of color [29]
oxidation method CuO; surface area= 143 (81%); COD (67%); TOC (64%)
m2 g− 1 adsorbable organic halides (61%);
and chlorophenolics (66%) was
obtained
Photocatalytic – solar murexide dye and Co and Co3O4 Microwave Co 15.53–31.00 (22.75) Highest degradation efficiency [30]
light erichrome blak-T (EBT) nm and (43.6%) towards murexide dye at
dye Co3O4 as 14.28–39.29 25 mg loading and 40 mins
(27.16) nm exposure time, while Co3O4
nanoparticles gave the maximum
degradation efficiency (39.4%) at
10 mg loading and 40 mins of
sunlight exposure in EBT
Photodegradation Phenol Cu (2 – 4%) doped Wet chemical method 22–26 nm Maximum degradation efficiency [31]
NiO = 75.2% (0.4 mol/L). In real
leather industry wastewater -
maximum degradation efficiency
= 85.7%; reaction time = 2.5 h
Wet oxidation Phenol NiO/CeO2–ZrO2 sonolysis 77 nm, 32.7 m 2 g-1 Removal of phenol increased with [32]
increasing catalyst loading from 4
to
9.0 g/l but further increase upto
10 g/l reduced the catalyst
reactivity
Photocatalytic (visible Acid Orange Ag (5%)-ZnO/MW- precipitation- 29–33 nm and 18 – 38.4 Maximum degradation efficiency [33]
light) CNT decomposition m2g− 1 was obtained at 3–9 pH. Also,
method Ag–ZnO/CNT(5)
nanophotocatalyst showed
apprecaible recyclability over
many separation cycles
Multi-repetitive methylene blue Co, Cu, Ni and Fe Swelling of hydrogel - Ni@AA-co-AM and Fe@AA-co- [34]
oxidative degradation (20%) on acrylic acid- and impregnation of AM nanocatalyst samples show
co-acrylamide (AA- nanoparticles highreusability, achieving near
co-AM) (80%) 100% methylene blue
hydrogel degradation
Reduction and Methylene Blue (MB) Au on Magnetic green method by an 11 – 13 nm Degradation reaction of azo [35]
Oxidation and Methyl Orange Fe3O4 @polyaniline active bioagent and dyeswith NaBH4 in presence of
(MO) co-precipitation the nanocatalyst is 1000–10000
process times faster than degradation
reaction without using the
catalyst
Wet air oxidation with Reactive Red 120 Fe-ZSM-5 hydrothermal 291 − 320 m2g− 1
98% decolorization was achieved [36]
heterogeneous (RR120) azo dye nanocatalyst technique and wet in 30 min and regeneration
electro-Fenton impregnation method process and provides more than
reaction 95% decolorization efficiency in
several batches
Photocatalytic Direct Blue 15 Fe-N-Ce-TiO2 sol–gel method TiO The removal efficiencies were [37]
degradation – visible 2 = 9.65 nm, TiO2-N = found to be higher in acidic pH
light 34.58 nm, TiO2-Fe= than basic pH. 100% removal of
21.65 nm, TiO2-Ce= dye at optimal conditions - pH =
14.4 nm, TiO2-Fe-Ce= 5.7; current intensity = 0.68 A;
8.65 nm, TiO2-N-Fe= initial dye concentration = 25
7.2 nm and TiO2-Fe-Ce- ppm; nanocatalyst dose = 10 mg/
N= cm2; reaction time = 1 h.
21.6 nm
Catalytic degradation methyl orange (MO), Al-MOF/Fe3O4/ mesoporous structure, Obtained removed of CIP = [38]
ciprofloxacin (CIP), PDA@Ag large surface area and 81.7%; NOR 80.1%; MO = 98.2%
norfloxacin (NOR) magnetic property at reaction time = 40 min; NaBH4
dose = 10 mM. The maximum
decolorization efficiency acieved
(continued on next page)
4
Table 1 (continued )
oxidizing agents
was 97.1% at high initial dye

concentration (150 mg/L)
Photo-Fenton process Orange II bentonite clay-based sol–gel and pillaring - Fe–B nanocatalyst has the [39]
(UV light) Fe nanocomposite method potential to be adopted in real
and Fe3+-doped TiO2 time effluent treatment in large
industrial scale applications as a
photo-Fenton heterogeneous
catalyst.
Photocatalysis using methylene blue (MB) star-shaped ZnO/Au precipitation method 22 nm With 40 mg of catalyst, 95% [40]
UV-A irradiation, and degradation of MB was achieved.
solar irradiation; In solar irradiation, ratio of MB to
sonocatalysis in dark catalyst controlled the
condition. degradation rate. Photoctalaysis
showed improved results.
Reduction of dyes rhodamine B (RhB), 4- Fe3O4/SiO2-Pr-S-Ag chemical 30–40 ± 5 nm, Degradation of the MB, 4-NP, and [41]
by NaBH4 nitrophenol (4-NP), and coprecipitation RhB by the nanocatalyst =
Methylene blue (MB) method 95–98%.
This nanocatalyst is highly
recyclable beacause the loss of
catalyst is negligible even after
eight reaction cycles.
Photocatalytic Acid orange 7 Fe3+ doped TiO2 Sol- gel method 30 nm, 50 m2g− 1
Maximum dye removal - 100% [42]
degradation (UV, under both UV and visible light
visible and solar light) source; 90% when solar light is
used. Dye degradation = 98.9%;
reaction time= 5 h. At reaction
time = 3 h; the conversion ratios
at
initial pH 3.0 (96%), 5.0 (87%)
and 9.0 (40%)
Sonocatalytic Methylene blue Cadmium selenide/ sonochemical- 20 nm, 10.42–22.5 The degradation efficiency = 99% [43]
degradation graphene quantum hydrothermal process. m2g− 1 achieved at catalyst loading = 1
dots (CdSe/GQDs) g/L; initial MB concentraion = 20
mg /L; pH = 9, and output power
= 200 W/L at ultrasonic
irradiation time = 90 min.
Degradation efficiency was
enhanced when K2S2O8 and H2O2
(enhancers) were added.
Photo Fenton process Methylene blue Cu-Mn porous silica two-step solvothermal 392 – 461 m2/g The maximum degradation of [44]
(UV–VIS radiation) supported synthesis and incipient methylene blue was ~80%
photocatalyst wetness impregnation attained at neutral pH with a dye
(CuMnKIL-2 with method concentration of 25 mg/L
Mn/Si = irradiated by halogen lamp (UV-
0.01, Mn/Cu = 0.06) Vis – 7% UV) for ~240 mins
Wet hydrogen peroxide Methylene blue 01MnKIL-2 (Si/Mn two-step solvothermal 10 – 20 nm The maximum TOC removal = [45]
catalytic oxidation ratio = 0.01) synthesis 81.7% at temperature = 25 ◦ C,
(WHPCO) pressure = 1 atm, stirrer speed =
320 rpm, catalyst loading = 400
mg/L, dye loading condition =
0.05 g/L, H2O2 concentration =
3.3 g/L. Optimum pH = 6–10
Photocatalaytic Methyl orange (MO) ZnO 1D necklace-like Hydrothermal process Diameter around 30–50 Degradation obtained = 57.29% [46]
degradation nanostructures (NNS) and calcination (At nm MO (2 times higher than
400 ◦ C for 30 mins) nanoflowers, 10 times higher than
nanosheets and 17 times higher
than hexagonal nanoplates); TOC
removal = 25.3% at photocatalyst
loading = 10 g/L; initial dye
concentration = 10 mg/L. Light
source - 6 W UV lamp; wavelength
= 465 nm.
Photocatalytic Methylene blue (MB) Hydrogenated TiO2 Hydrogenation in Shell thickness ~ 2.8 nm Catalyst irradiation time = 2.5 h, [47]
degradation (visible nanoparticles (novel corundum tube at the TOC removal = 81%.
light) core shell structure) 5500 C Experimental solution - 100 mL; 5
mgL− 1 with illumination source -
500 W Xe lamp (PL-XQ 500 W).
This hydrogenated TiO2 showed
400% more efficiency than
pristine
TiO2
Photocatalytic Methylene blue ZnO nanorod arrays Integrated synthesis Surface area = 597 – Degradation efficiency = 77.5%; [48]
degradation on activated carbon approach involving a 689 m2/g mineralization levels = 55.0% at
fibers sol-gel followed by a highest reusable condions –
Reaction volume = 300 mL; initial
5
Table 1 (continued )
oxidizing agents
hydrothermal dye concentration = 5 mg\L;

synthesis step catalyst dosage = 45 mg; reaction
time = 2 h.
5.1.1. Titanium and Titanium Oxides (TiOx)

Table 2
TiOx is one of the most widely used materials in AOPs as catalysts
Some of the listed advantages and disadvantages of TiO2 nanocatalyst in
and catalytic supports for noble metals such as Au, Rh, Pt, Ag and Pd.
wastewater treatment [57,58].
TiOx can be of many shapes i.e. TiO2 nanotube, nanosheet and nano
fiber. It is also doped with various other metals and metal oxides such as Advantages Disadvantages
Ce & Ce-oxide, Al-oxides and Fe & Fe-oxide [1]. TiO2 is found in 3 • Wide Band gap under UV (3.2 eV) • Small specific area when impregnated
crystalline forms – brookite (orthorhombic), anatase and rutile (tetrag • Thermal stability of TiO2 anatase • Low quantum efficiency when
upto 900 ◦ C impregnated
onal) [54]. The positive holes of TiO2 have a strong oxidation potential
• High physical stability • Low adsorption abilities when
which helps in production of hydroxyl radicals from water by hetero • High refractive index impregnated
geneous photo catalysis. This was first discovered by Fujishima and • Non-toxic • Inadequacy for continuous processing
explored the reaction mechanism as. • Long term photo stability • High cost and difficulties in separating
• Good mechanical resistance in catalyst from the reaction media
TiO2 + ɦυ → TiO2 (ƛ+ + e-) (Reaction 1) acidic and oxidative medium • Poor regenerability in non-impregnated
form
+ +
TiO2 (ƛ ) + H2O → TiO2 + •OH + H
TiO2 (ƛ+) + OH− → TiO2 + •OH on organic contaminants in wastewater is known as Fenton reagent.
While oxidizing tartaric acid in the presence of Fe2+ and H2O2, this acid
•OH + organic pollutants → CO2 + H2O
vanished into CO2 and H2O [5–7,13,32,59]. Best and efficient removals
TiO2 + (e- + O2) → TiO2 + •O−2 of any pollutant at acidic pH condition (pH~3.0) in wastewater are
reported in Fenton’s process. Only a small fraction of Fe2+ can be uti
• −
O2 + 2 H2O → 2 •OH + 2OH− lized to carry-on the catalytic process and this can be regenerated in the
• − reactor section. There are various methods for preparation of Fe Nano
O2 + 2OH− → 2 •OH + O2
particles (mostly spherical) [58]– Pyrolysis, Gas deposition, Bulk solu
•OH + organic pollutants → CO2 + H2O tion, Sol gel and micro emulsion methods (spherical and cubic) which
are adopted as per size and application requirements.
The above mechanism (Reaction 1) is called Honda-Fujushima effect, Classical mechanism of the Fenton process is a common straight
photo activation of positive holes in TiO2 takes place to act as a catalyst forward redox reaction, in which the ferrous ions are oxidized to ferric
which is not consumed until photo bleaching happens. Thus, it provides ions and H2O2 is reduced/decomposed to a hydroxyl ion and radical
high regenerability and low emission except water and carbon dioxide [56].
[2].
TiNTs (Titanium nanotubes) provides a specific surface area of 155 Fe2+ + H2O2→ Fe3++ •OH + HO- (Reaction 2)
m2/g and pore volume of 0.57 cm3/g. However the above mentioned
Hydroxyl radicals are generated through the mechanism explained in
properties reduce on impregnation of Cu [3]. In UV Photocatalytic
Reaction 2, but each ferrous ion generates only one •OH radical. The
degradation of Amaranth (AM) Azo dye which reported on Ti nanotube
Fe3+ ion generated in Reaction 1 is reduced back to Fe2+ ion during the
based treatment [55]. Optimum conditions of initial TiO2 dose of 160
reaction, due to the availability of second H2O2 molecule (Reaction 3),
mg/L and UV radiation (wavelength of 254 nm) of 10 mW/cm2 was
however, the reaction requires stoichiometric amounts of Fe2+ ion to
maintained during the process. For 100 min illumination period, the
attain maximum efficiency and regenerability and it is relatively slow
decolourisation extents were 38% and 64% for TiO2 and TiO2
(at optimum pH~3) [56].
+UV+H2O2 respectively.
Visible light photo degradation of dyes: TiO2 is sensitized with some Fe3+ + H2O2 + H2O → Fe2+ + HO•2 + H3O+ (Reaction 3)
dyes like – erythrosine B, Thyonine, substituted and unsubstituted pyr
3+ 2+
idine and phthalocyanine. The absorption wavelength of TiO2 that is HO•2→ +
Fe + Fe + H + O2
sensitized via an appropriate dye molecule can be stretched to visible
In order to speed up the reaction, regeneration of ferrous ion is
region because of the property of the dye molecule to absorb the visible
accelerated by addition of phenolic compounds especially dihydroxyl
light to reach a higher energy level. Surface sensitization or excitation of
benzene (DHBs) which has the ability to reduce ferric ions providing
TiO2 via electron transfer by physisorbed or chemisorbed dye molecules
better efficiency in the remediation process[6,27].
can.
Though there are many studies reported relevant to Fe-based
oxidation, it can be highlighted with BR18 and AR88 dyes degrada
i. enhances the efficiency of the excitation processes
tion process [46]. Ordinary Fenton reaction is carried out by addition of
ii. Increases the optimum wavelength range via excitation of the dye
Magnetite Nanoparticles coated on borosilicate glass. For 0.1 mM dye
molecule (sensitizer) followed by transfer of electrons between the
concentration- 10 mM H2O2 concentration and 2 g/l Magnetite NP
sensitizer and TiO2 surface.
concentration has considered optimal due to achievement of adequate
oxidative radical formation and elimination of the scavenging effects.
Some of the merits and demerits of TiO2 as a nanocatalyst are pro
Fenton oxidation of BR18, optimal pH condition was 3.0 and for AR88 it
vided in Table 2 [54,56].
was 6.0. About 78.3% of colour removal efficiency was obtained.
Similarly, degradation of azo dye AR18 have also reported in the liter
5.1.2. Ferrous and ferrous oxides
ature [49]. SBR and enhanced Fenton reaction was carried out, to
One of the effective reagents which have high destructive capability
remove 99% of the dye and 97% of COD. The Fenton reaction was
6
enhanced by using H2O2 and zero valent iron (ZVI) with ultrasonic ra 5.1.4. Manganese and manganese oxide
diation. Factors to be noted during fenton reactions are:- Among metal oxides, nanosized manganese oxide (MnO) is a very
common part of aquifers, sediments, and soil [29]. Naturally, these are
• Optimal pH range is 2.5–3.5 [60]. present in colloidal or discrete particles and are found blended with iron
• Disproportionation and decomposition of H2O2 would exhaust •OH or other minerals. They show huge potential in regulating environ
leading to reduction in H2O2 utilization [60]. mental pollution levels via photochemical degradation, adsorption, and
• Ferric ions are easily precipitated as iron and it becomes difficult to catalytic pathways. For example, they have been shown to have good
recover the iron source and reduces the overall efficiency of the re ability to scavenge metal ions and dyes due to their ability to possess
action [60]. high specific surface areas (SSA), low or medium surface charge, and
• Production of iron containing sludge (slow regeneration) and loss of comparatively smaller particle volume, having amorphous and poly
catalyst [61]. morphous nature. MnO is a very common naturally occurring oxidant,
• Zero valent Iron has less reactivity due to its intrinsic passive layer and it occurs in various physical forms mostly of layered or tunnel
[57]. structures comprising of octahedral MnO6. Mn-Oxide mineral materials
have been applied for numerous applications including ion-exchange,
5.1.3. Aluminium and Aluminium Oxides batteries and also as catalysts for dye degradation. As naturally occur
Aluminium is the most abundant metal on the earth’s crust and if ring MnOx contains various impurities, their effectiveness as sorbents to
utilized well it could be an efficient and effective catalyst. Al2O3 remove particular dyes maybe affected significantly, depending on their
(Aluminium oxide or Alumina) provides diverse applications in metal structure and composition. Therefore, synthesized MnO minerals with
lurgy, water treatment, ceramic industry, manufacture of zeolites, cos known composition and structure have been utilized by many re
metics, electronics, fire retardant and also smoke suppressant. It also searchers to more effectively understand and estimate the ability of MnO
provides as an efficient catalyst and catalyst support. It has varied pore minerals as sorbents to remove dyes from solution. Besides, manganese
sizes with a different class of pore diameter in the molecular level of the oxide composites or coatings can play a major role in redox transition
zeolites framework. In catalyst ozonation processes which consists of zones [61]. It was found that the decomposition of H2O2 using β-MnO2
γ-Al2O3 nanoparticles are widely used due to the interactions of ozone from pyrolusite could produce active free radicals such as HO•2 and •O2.
and •OH groups made popular in treating landfill leachates, bromaminic Using these advantages, the MnO2 particles have been proved to be
acid, benzene, 4-chlorophenol, benzene, 2,4-methylphenol, cipro useful for performing AOPs and ABS (adsorptive bubble separation)
floacin, bromaminic acid, 2-isopropyl-3-methoxypyrazine and reverse simultaneously known as advanced ABS system with addition of H2O2
osmosis rejects organic compound [62]. and surfactant [63]. The peroxide can reduce Mn(IV) to Mn(II) at the
Zero valent aluminium (ZVAl) provides high specific surface area surface of MnO2 and generate oxygen gas. The detailed mechanism of
and surface reactivity compared to other metal catalysts. It also has the H2O2 activation on Mn surface is represented in Fig. 1 [63]. The MnO2
ability to generate both •OH and SO•− 4 radicals for water treatment [57] has chemisorbed oxygen on the surface which is very much reactive and
and its mechanism is reported as. possess high mobility because of its loose surface bonding. This kind of
lattice oxygen (O-2) can be present in an ionized state and increases the
2ZVAl + 3 O2 + 6 H+ → 2Al3 + 3 H2O2 (Reaction 4) efficiency of decomposition of H2O2. Through the following reaction
2ZVAl + 6 O2 → 2Al 3+
+6O •2- (reaction 5), O2 gas is produced from the reaction between MnO2 and
H2O2.
6 O•2− + 6 H+ → 6OOH•
MnO2 + H2O2 → MnO + H2O + O2 (Reaction 5)
6OOH• → 3 O2 + 3 H2O2
H2O2 + O−2 → O2 + − OH + •OH
ZVAl + 3 H2O2 → Al3+ + 3OH− + 3 •OH
Recently, the oxidation of methylene blue (MB) using MnO has been
ZVAl + 3 H2O2 → Al3+ + 3 H2O•2- reported by few articles [29,63,56]. Here the MnO2 was coated on Fe3O4
with a simple hydrothermal process producing MnO2-Fe3O4 nano
3 H2O• 2− → 3OH− + 3 •OH
composites [64]. This reduced the problem of removing the MnO2
In the above reactions there is no need of H2O2 to produce •OH free catalyst by filtration and magnetic separation can be used to efficiently
radicals, instead O2 and acidic water is enough. The performance gets remove the catalyst. The classical process of AOP was slightly modified
affected by pH, initial pollutant concentration and catalyst concentra by adding surfactants to produce micro bubbles which are more efficient
tion. The removal of Orange G and Acid orange 7 from aqueous solution in ion floatation as they rise slower with higher contact with the
was reported by using Al based catalyst. The Al-based nanoparticles chemicals present in the solution.
wastewater treatment has many advantages and disadvantages and is
listed in Table 3 [57]. 5.1.5. Copper and copper oxide
As discussed previously, Fenton processes were determined to be
highly effective in oxidation of recalcitrant organic molecules but it still
had its own disadvantages like slow catalyst regeneration and pH re
strictions which limit the process to only acidic conditions which results
Table 3 in loss of Fe2+ ions and production of large amounts of iron sludge (loss
Some of the listed advantages and disadvantages of Al nanocatalyst in waste
of catalyst). These disadvantages were overcome by Cu(I) catalyst for
water treatment [55].
Fenton like reactions and was found to be more efficient than classic
Advantages Disadvantages Fenton process since it’s reaction rate with H2O2 is 4 × 105 /Ms which
• ZVAl provides high surface • Risk of deposition of Al-oxide on Al in ZVAl/ was approximately 10,000 times more than Fe(II)/H2O2 (rate is Fe(II)/
area and surface reactivity O2 causing reduction in performance H2O2 = 63–76 /Ms) and hence Cu(I) was considered to be more efficient
• High availability of Al (about • Works efficiently only inside a limited pH
than Fe(II) in neutral and alkaline pH conditions. Additionally, Cu(I)
8% of earth’s crust range (acidic)
• In situ preparation of H2O2, • Low mineralization efficiency could also facilitate generation of molecular oxygen more effectively
Therefore cost efficient than Fe(II) for in situ generation of reactive oxygen species (ROS).
• High pollutant removal However, the rate of regeneration of Cu(I) is slow which would still
efficiency hinder the neutral copper cycle and disrupt the Fenton-like reactions but
7
Fig. 1. Schematic diagram of H2O2 activation by the catalyst [59].
hydroxylamine could be utilised to keep up the neutral cycle in Cu(II)/ scaling-up from pilot study [78,79]. It is recommended to activate the
O2 systems [65]. 4 by heterogeneous catalyst compared to ultrasonic, thermal and
SO•−
CuO has show as effective catalyst and promoter for oxidation pro microwave methods. Compared to •OH method of oxidation, SO•− 4 has
cess. When CuO impregnated with iron, induced the Fenton mechanism merits of high oxidation potential, high reactivity with unsaturated
to a significant rate in alkaline pH. Similarly, CuO has recently noticed bonds or aromatic π-bond electrons of organic compounds, reactive in
for reusable metal oxides with Cu2+ on alkaline H2O2 and NaOH con wide pH range of 2–8 and better mass transfer and contact with organic
centration by inducing copper peroxide intermediate [8]. Anushree compounds due to higher half life period [88].
et al. indicated that CuO has en route the oxidation mechanism through
carboxylic from the alkyl group into biodegradable compounds. Drastic
reduction of colour and COD are indication in high efficient removal of 6.1. Transition metals
POP in wastewater at wet air oxidation process [34].
The application of Cu-based degradation of Rhodamine-B (RhB) by The concern on the transition metals in catalyst application mainly
Cu/Fe/CDBQ/H2O2 (CBDQ - 2,5-dihydroxy-1,4-benzoquinone laid to cost, toxicity, availability and environmental friendliness. Here,
restricted in cyclodextrin) has been reported [66]. Ru-based materials can be expensive and Co- or Cu-based catalyst can
leach into toxic metals which might concern the health hazardous effect.
6. Sulfate radical Similarly, Mn-based materials show low toxicity and environmental
friendliness in applying at oxidation catalyst, but it can affect the acti
Generally, peroxymonosulfate (PMS) and peroxydisulfate (PDS) are vation mechanism in the presence of dissolved oxygen.
organic decomposition compounds with persulfates of peroxide bonds
split into sulfate species. This bond cleavage induces the production of 6.1.1. Cobalt and cobalt oxide catalyst
highly reactive and unstable radicals such as SO•− 4 and •OH radicals There are five Cobalt oxides have been investigated - CoO, CoO(OH),
using external energy supply or catalytic activity. To avoid reduce CoO2, Co2O3 and Co3O4, in which CoO2 is thermally unstable. In the
external energy consumption in the process, heterogeneous catalytic treatment processes, CoO and Co3O4 are frequently investigated with
system are employed which has easy recoverable and recyclable into PMS activation system. Though the study of CoO/PMS system, dissolv
treatment processes [67–70]. Removals of organic pollutant with min ing of CoO in water increases the rate of dissociation of Co in homoge
imum environmental effect like metal leaching in the water treatment nous system and leached out. However, Co3O4/PMS can participate in
are the main desire in the objective to use heterogeneous materials. redox reaction in the form of Co2 + ions and further crystal lattice can
Hence, the summarized organic pollutant which removed by persulfate reformulated into Co3O4 by Co3+ ions. This enables us to investigate
mechanism are represented in Table 4 [71–85]. There is intensive further synthesis of Co nanoparticles using thermal decomposition,
research on-going to remove contaminants by activating perox polymer combustion, sol-gel and hydrothermal methods. Top-down
ymonosulfate (PMS) and peroxydisulfate (PDS) using transition metals synthesis of Co3O4 from decomposition from inorganic or organome
like Co, Ag, Mn, Cu and Ru based catalysts [70,86,87]. Owing to ad tallic precursors is effective but exhibit in an uncontrolled distribution of
vantages of less energy requirement, high reactivity and ease of size or morphology. It contains incomplete decomposition of precursors
mixed with phase transformed Co in the form of CoO and Co3O4
8
Table 4
Catalytic process using nanoparticle as catalyst using oxidation process by sulfate radicals on dye effluent.
Assisted process Compounds Catalyst and Synthesis method Degradation mechanism Ref
oxidizing agents
Catalytic degradation Aniline, metoprolol CoFe2O4 - The degradation efficiency obtained for 2-nitroaniline ~ [70]
nanocatalyst 59.8%; sulfapyridine ~ 65.5%; aniline ~ 67.5%; X-3B ~
78.0% and 4-chloroaniline ~ 92.4%. metoprolol removal
> 80 at initial pH = 10.0. Better results at alkaline pH
Catalytic Degradation Methylene Blue Mesoporous Cobalt - At reaction temperature = 298 K; PMS loading = 0.8 g/L; no [71]
Silicate (CoSiOx) of cycles = 5, a comparitively low degradation rate is
observed. Degradation efficiency = 73.5% when EtOH and
TBA (scavengers) were used.
Catalytic Degradation Orange II Co-Mn catalyst _ The degradation reaction was carried out in dark condition [72]
activated by with a dosage of 1–5 g/L of bisulfate. The reaction was
NaHSO4 significantly accelerated and the efficiency ranged from 67%
to 93%. 3–5 g/L dosage had no effect
Decontamination by Methylene blue Carbon nanotubes - CNT adsorption capacity (310 K) = 132.6 mg/g. The blending [73]
adsorption (MB), Neutral Red (CNTs) of Fe2O3 nanoparticles with MWCNTs showed better removal
(NR) of NR along with MB. The maximum adsorption capacities for
MB = 42.3 mg/g and NR = 77.5 mg/g.
Enhanced adsorption Methylene Blue 3D P25-graphene - This hydrogel shows better degradation efficiency compared [74]
hydrogel to pure P25 and P25-MWCNT graphene. 100% dye
degradation with UV light irradiation; reaction time. While for
100% degradation - reaction time = 180 min for pure P25 and
P25-MWCNT graphene.
Degradation by electo- Orange II Co-Fe catalyst - Dye degradation efficiency increased from 18.2% to 95.6%; [75]
regenerated cathode PS decomposition increased from 14.9% to 42.3% in Fe-Co/
reduction of Fe3+ SBA-15/PS system.
Catalytic degradation using Acid Orange 7 MnFe-LDH (Layered Co-precipitation In MnFe-LDH(1:1)/PMS system, dye degradation efficiency [76]
PMS system (AO7) double hydroxide) = 97.56%; reaction time = 30 min. Wheareas, in Mn(II)
+ Fe3+/PMS system (same MnFe-LDH(1:1) volume) - dye
degradation efficiency = 8.64%. Inference from results -
MnFe-LDH is a better activator of PMS.
Catalytic degradation using Rhodamine-B Mn3O4/ZIF-8 Hydrothermal The degradation of Rh-B in the absence of quenchers using a [77]
PMS system + solvothermal Mn3O4/ZIF-8/PMS system reaches upto ~86.4% and with
quenchers – EtOH (EtOH:PMS=2000:1) and TBA (TBA:
PMS=4000:1) the degradation was decreased to 74% and 56%
respectively.
Catalytic degradation using Acid orange 7 CuO/OMS-2 Refluxing method In CuO/ PMS and Cu2+/ PMS systems - dye degradation [78]
PMS system efficiency was 56% and 49% respectively at reaction time
= 0.5 h. In OMS-2/ PMS systems, dye degradation = 52% at
acidic pH. In Cu-OMS-2/ PMS systems, dye degradation
efficiency = 93%; reaction time = 20 min
Catalytic degradation using Rhodamine B α-MnO2 Hydrothermal method Dye degradation efficiency = 87%; COD removal = 61% at [79]
PMS system reaction time = 30 min and degradation efficiency = 99%;
COD removal = 86% at reaction time = 60 min. The dye
degradation was higher than mineralization. In the third run,
the dye degradation = 97% at reaction time = 30 min
Catalytic degradation using Rhodamine B γ- Fe2O3/Mn3O4 Hydrothermal method It was observed that the degradation rate of increased with [80]
PMS system (RhB) increased concentrations of γ-Fe2O3/Mn3O4 nanocomposites,
because of the significant rise in the active sites available for
activation of persulfate. Maximum dye degradation efficiency
= 95.6% at initial catalyst concentration = 50 mg/L; reaction
time = 150 mins.
Catalytic degradation using Acid Red 73 (AR- MnO2/Fe3O4/ silica Thermal decomposition Maximum dye degradation efficiency = 98.38% at reaction [81]
PMS system 73) nanofiber + Hydrothermal method time = 30; MnO2/Fe3O4/SNF catalyst usage. Whereas, dye
composite degradation efficiency for MnO2/Fe3O4 = 88.4%, MnO2
+Fe3O4/SNF = 58.20%, MnO2 = 70.92% and Fe3O4/SNF
= 23.35%.
Catalytic degradation using Acid Orange 7 OMS-2/Carbon Refluxing method In presence of only OC-2 (by adsorption) - dye removal [82]
PMS system (AO7) nanofiber (OC-2) = 14%; reaction time = 20 min. In presence of only PMS, - dye
removal was very low min. when both OC-2 and PMS are
present, the dye degradation = 98% reaction time = 20 mins
Catalytic degradation using Acid Orange 7 MnO2 Hydrothermal method An electic field was applied and as the voltage increased from [83]
PMS system 1 to 6 V, the decolorisation efficiency increased form
74.4–98.1% at pH 3.0
Catalytic degradation using Acid Orange G Co-Mn LDH Co-precipitation The degradation efficiency of the catalyst obtained was 100% [84]
PMS system in 120 s which is far better than many similar combinations.
FeCo LDH – 80% in 240 s and CoMn LDH – 60% in 240 s
nanoparticles. Different types of Co nanoparticles such as nanospheres, Bottom-up synthesis of Co3O4 by sol-gel synthesis can form nano
nanocubes, nanorods, nanosheets and nanorings are synthesised by sphere or nanocube crystals with size of 60–80 nm. It is proved to have
Co3O4 by mechnochemical process, molten salt synthesis and γ-ray increased crystalline shape with increase in calcination temperature but
irradiation redox mechanism. Similarly, combination of cobalt nitrate decrease in surface area. Similarly, cobalt-ferrite (CoFe2O4) of spherical
and polymer (polyvinyl alcohol) can produce cubic structure crystal aggregated nanoparticles showed similar cryatallinity nature with
with sixe 33 nm, which has inclined effective over the oxidation process. calcination temperature, in which coalescence of CoFe2O4 with
9
decreased surface area can diminish the PMS activation mechanism. In –MnOx and MnOx hybrids & carbonaceous, so it may contain various
addition, co-precipitation is another method which synthesises the other elements and impurities due to which there may be significant
nanoparticles directly without further processing, but to decrease the reduction in its reactivity. The physical and chemical properties of MnOx
particle size and suppress the particle growth on some extent need a might be impacted by the reaction conditions – reaction time, reaction
capping agents to control the size. Hydrothermal synthesis of Co3O4 is temperature, and the availability of oxidant or reductant. For example,
focused on synthesis of nanoparticles with tunable morphology based on δ-MnO2, δ-MnO2 and α-MnO2 were obtained when MnOx was heated at
adjusting parameters such as temperature, reaction time, surfactant, 60, 100, and 110 ◦ C respectively; here the temperature change affects
templates and precursors. There are different shapes and sizes of the surface area and structure of the obtained MnOx. The changes in
nanoparticles like nanosheets, nanocubes, nanorodes and nanoflakes in structural properties due to the changes in reaction conditions must be
controlled crystal growth by employing the surfactants and ligands. It considered to better understand and predict the reactivity and mecha
indicates major merits like low cost, high reproducibility and short re nisms of generation of sulphate radicals (both PMS and PDS) by Man
action time compared to other synthesis methods. Similarly, microwave- ganese based catalysts. The Mn based nanocatalyst synthesis methods
assisted hydrothermal method with high energy efficiency proved as include – hydrothermal, solvothermal, biosynthesis, solgel, hard tem
effective Co3O4 nanoparticles synthesis method. Co3O4 nanoparticles plate and precipitation methods [91]. The activation mechanism of PMS
with diverse morphologies can be synthesized using adjusted reaction by MnOx [92] has been reported as.
parameters [89,90]. The detailed activation of PMS and PDS using CoO
is represented in Fig. 2. HSO−5 + 2MnO →SO•− −
5 + OH + Mn2O3 (Reaction 7)
Co2+ + OH− → CoOH+ (Reaction 6) HSO−5 + Mn2O3 → SO•−

4
+
+ H + 2MnO
Co2+ + H2O → CoOH+ + H+ SO•−

4 +H2O → HO + H + SO2−
•
4
+
2−
SO•− − •
4 + HO → HO + SO4
CoOH+ + HSO−5 → CoO+ + SO•−
4 + H2O
2−
SO−4 + H2O/OH− ↔•OH+ SO42− SO•− −
5 + e → SO5
2−
SO•− SO•− −
4 + e → SO4
4 /•OH + organic contaminants → degradation products (CO2 + H2O)
CoO+ + 2 H+ → Co3+ + H2O 2HO•→ 1∕12O2+ HO
Moreover, studies on usage of MnOx other than MnO2 such as MnO,

Co3+ + HSO−5 → Co2+ + SO−5 + H+
Mn2O3 and Mn3O4 for PMS activation have also been conducted. The
The generation of CoOH+ in Reaction 6 is the rate determining catalytic activity of MnOx on PMS activation was found to be dependent
(slowest) step; thus, the functional groups on the surface of the silicates on the oxidation number of Mn in the particular MnOx - MnO2 < Mn3O4
such as hydroxyl group accelerates the sulphate radical production via < MnO < Mn2O3. Different shapes of Mn2O3 also had different effects on
PMS activation, due to which CoSiOx shoes extraordinary catalytic catalytic activity, with the order Mn2O3 (truncated) < Mn2O3 (octahe
behaviour compared to other catalysts [72]. dral) < Mn2O3 (cubic) [45].
6.1.2. Manganese catalyst HSO−5 + 2MnO → SO•− +

4 + H + Mn2O3 (Reaction 8)
Manganese is said to overcome some of the disadvantages found in HSO−5 + 2Mn3O4→ SO•−
4
+
+ H + 3 Mn2O3
Co and Cu catalysts in activating PDS/PMS radicals. The Co and Cu
based catalysts might raise health issues because of the leeching of toxic The catalytic mechanism of Co-Mn catalyst in the degradation of
metal ions into the aqueous phase and Ru based catalysts which are Orange II dye in the absence of light and NaHSO3 (sulphate radical
costly. Unlike the above mentioned catalysts, Mn is not very toxic, source) was studied [84]. It was evident that some new oxidative species
plenty available in nature and environmentally safe. Mn based materials were generated to enhance the degradation efficiency of Orange II;
naturally occur in various forms with different chemical compositions Reaction 9 explains the dye degradation mechanism in detail.
Fig. 2. Activation of PMS and PDS by Co in wastewater treatment mechanism [71].
10
SO•− •−
3 +O2 → SO5 (Reaction 9) structure, the carbon involves in separation, catalysis, adsorption,
electrolysis and membranes, especially for large organic pollutant
SO•− - •− 2- involving processes [94].
5 + HSO3 → SO4 + SO4
Suitable pore size and electrical conductivity properties can
emphasize the carbon based capacitive deionization electrodes in suit
2-
SO•−
4 + H2O → •OH + SO4 + H
+
able electrolysis of electrosorption process have proved as high energy

SO•−
3 / •OH + Dyes → Product (CO2& H2O)
saving process. Intensive research on different electrodes are carried
The degradation of Orange II was found to increase significantly with below the breakdown voltage of water (1.23 V) onto the porous
from 67% to 93% when bisulphate concentration was varied between 1 materials induced the accumulation of ions or charged compounds onto
and 3 g/L. The simple reason for this result would be as the availability the polarized electrodes in aqueous solution [95]. Here, cathode elec
of reagent increases, oxidative species generation rate increases. How trodes with negative polarization on Multi-walled Carbon Nanotube
ever, when the bisulphate concentration was varied between 3 and 5 g/ (MWCNT) can electrosorption of aniline have low operating coast than
L, the changes in degradation efficiencies obtained where negligible. simple Pt cathode. Also, Anode MWCNT used to PDS activation for
This could be because of the limiting reaction rate of Co-Mn with removal of acyclovir and phenol shows a stabile electrodes material.
bisulphate. This Anode show higher degradation efficiency due to the electrostatic
attraction between S2O2- 8 anions and anode [15,96–102].
6.1.3. Carbonaceous catalyst
Using heterogeneous metals as oxidation-AOP has been widely 6.1.3.2. Carbon nanotubes. Carbon nanotubes (CNTs) have a lot of ap
studied, but due to metal leaching in the water treatment can induce plications and roles to play in wastewater purification methods and have
hazardous stage of contaminant. The toxicity affects the water, partic been largely adopted as adsorbents for many different inorganic, organic
ularly treated or reusable water has to follow the limit of toxic con wastewater contaminants. In addition to that, they are also used in
taminants. This can be achieved only through using metal-free oxidising electrocatalysis, and photocatalysis systems. CNTs are allotropes of
catalyst or metals. In such case, it is widely popular to identify the non- carbon and are broadly divided into two categories - single-walled
metal persulfate activator for the removal of organic pollutant from the (SWCNTs) and multi-walled CNTs (MWCNTs), which are distinguished
wastewater treatment techniques. Carbon-based or carbonaceous cata by the number of layers (either one or many) making up the nanotubes.
lyst in persulfate activation by SO•− 4 radicals has achieved high effi CNTs have grasped the curiosity of numerous researchers in the field of
ciencies using reduced graphene oxide in AOP. Later, metal-free carbon nanotechnology due to their excellent electronic and mechanical prop
of nanodiamond, nanotube, nanofibre, graphene-based carbon and erties, potential applications, and high chemical and thermal stability.
mesopores carbon are involved with various dimensional pore structure Due to their high specific surface area, single/multi layered arrange
showed as good catalyst in terms of PDS activation. Generally, strong ment, and hollow nature, they form a perfect adsorbent material. They
adsorption capacity, metal-free catalytic activity, good efficiency and are industrially used as promoters for various reactions, also in desali
stability are the merits to effectively utilizing carbonaceous catalyst in nation of brackish and sea water, reduction of various microbes and
AOP. Mainly two types of carbon NPs such as 1D, 2D and 3D carbon pollutants. Most pollutants adsorb on the inner and outer surfaces rather
nanomaterials are commonly employed in AOP. than the peripheral groove and interstitial channels of the CNTs. Addi
However the practical difficulty in recovery of carbon powder at the tion of functional groups to the CNTs enhances their chemical reactivity,
post-treatment process hinders the material involvement and usage. and facilitates adsorption of various contaminants. Methods for CNT
Recently, extruded carbon with binder was used as catalyst (carboca functionalization include treatment with covalent chemical agents, non-
talyst) pellets in organic treatment or as electrodes in electrosorption at covalent wrapping and endohedral filling. The interaction forces be
an electrochemical method of inorganic and organic compounds which tween the CNTs and pollutants include- p–p electron coupling, mesopore
are of growing interest. filling, hydrophobic interactions, electrostatic interactions, ion ex
change, hydrogen bonding, and covalent bonding. Several studies where
6.1.3.1. Carbocatalysts. Carbocatalysts are 3D carbon materials without CNTs were adopted for adsorption of various contaminants including
metals have amorphous nature with containing both sp2 and sp3 hy but not limited to cadmium, 1,2-dichlorobenzene (DCB), and lead from
bridized carbon in mixed form, such as activated carbon, mesoporous water. The major limitation of using CNTs for contaminant removal is
carbon and biochar [74,87]. scaling up to a pilot studies or large-scale industrial system [103].
Ordered mesoporous carbon, activated carbon (AC) and biochar (BC) The effect of various system pH and operating on the adsorption
are 3D bulk carbon materials that exist in amorphous form (consisting of efficiency of MWCNTs to remove procion red MX-5B from aqueous so
both sp2 and sp3 hybridized carbon). Due to the fact that they are very lution. The maximum adsorption capacity was found to be 44.64 mg/g
cost efficient and huge availability of carbon precursor materials, they for MWCNTs without any surface modifications. The adsorption of dye
are considered as one of the best choices for persulfate AOPs in appli on CNTs increased with a decrease in pH or temperature [75].
cations that involve environmental safety and health aspects. Particu Elimination of both cationic and anionic dyes (Neutral Red, methy
larly, BC of sludge has shown highest efficiency of 85% removal within lene blue and Orange II (OII)) from aqueous solution using mixture of
2 h of active catalytic process [48]. While, increasing pyrolysis tem carbon nanotubes and Fe2O3 nanoparticles were investigated in detail
perature and structure of biomass components, the catalytic activity has [104]. They possessed an excellent adsorption capacity of 132.6 mg/g at
been significantly modified. When pyrolysis the sludge at inert atmo an operating temperature of 310 K. From the obtained final results, it is
sphere and carbonisation temperature of 600 ◦ C show 100% bisphenol A inferred that MWCNTs could be utilised to effectively eliminate both
degradation while compared to 400 and 800 ◦ C carbonisation temper anionic and cationic dyes from aqueous solutions.
ature [85]. Biomass has pyrolysis into AC and BC at various carbon
isation temperatures has low efficiency than sludge based carbon 6.1.3.3. Graphene and graphene oxide. Graphene has gained popularity
catalyst. Similarly sludge carbon pyrolysis with partial oxygen has among the researchers due to its inclusion in the Nobel Prize winning
produced low activity catalyst than others as reported by Huang et al. research in 2010 by Geim and Novoselov. It is also known as ‘super
[93]. material’ due to its exceptional optical, mechanical, thermal and elec
OMC and AC are most popular due to their versatile applications and tronic properties. It also possesses an astonishing theoretical surface
they are economically viable for wastewater treatment. Due to their area of 2620 m2/g although practically this is difficult to achieve. These
unique structure, large and tuneable pore channels in mesoporous properties have led the scientists to research into its application in
11
transistors, electrodes, bio devices and many more electronic and non Table 5
electronic applications. Graphene can is actually a monolayer graphite Treatment efficiency data of other processes for comparison with AOPs.
that can be fabricated from graphite using numerous of methods. Geim S.no Method of treatment Compound (s) Remarks Ref
et al. was able to fabricate graphene using scotch tape method where the
1 Adsorption by CNTs Reactive Red Factors including [108]
layers of graphite were continuously separated until they obtained 120 (RR 120) efficiency adsorbent
monolayer and the unique properties of the obtained monolayer gra dose, pH, the initial
phene were extensively studied [105]. However this particular method dye concentration &
is obviously not suitable for the production of graphene on a large in the dye adsorbent
contact time had
dustrial scale. For facilitation of large scale production of graphene, one significant impact on
chemical method is by the oxidation and subsequent reduction of removal efficiency.
graphite. The oxidation of graphite gives graphitic oxide, which in turn The dye removal
can be chemically treated to produce graphene oxide (GO). The subse efficiency = 89% at
initial concentrations
quent reduction of graphene oxide results in formation of monolayer
- 10–200 mg/L.
graphene or reduced graphene oxide. Graphene and graphene oxide are 2 i. Coagulation by Combination In coagulation [109]
both monolayer forms of hexagonally arranged carbon, the main poly aluminium of dyes (real process COD removal
distinction is the hybridisation of carbon. Graphene is formed purely by chloride (PAC) time = 40%, BOD5
sp2 hybridised carbon atoms while on the contrary, the oxygen or oxide ii. Electro wastewater removal = 34%, TSS
coagulation sample) removal = 23.7%,
functional group present in graphene oxide introduces a fraction of sp3 iii. Adsorption using and dye removal
carbon atoms to the material. The abundance of oxygen on GO in various pistachio nut efficiency = 44.5% at
sites gives the material its ability for further functionalization and shell ash (PNSA) PAC concentration
tethering. Chemically modified graphenes (CMGs) are most commonly = 30 mg/L. In
electro coagulation
synthesised by utilising the epoxy or carboxylic groups on the GO sur
process, COD
face. Reacting the carboxylic groups with reagents such as thionyl removal = 93.1%,
chloride, 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide and N, BOD5 removal
N-dicyclohexylcarbodiimide help in formation of amide or ester link = 88.8%, and dye
ages respectively. Simple ring opening of the epoxy group by the addi removal = 98.6% at
voltage applied
tion of amines can alter the CMG properties such as dispersability and
= 60 V. In combined
stability according to the type of amine used. The photocatalytic prop process, COD
erties of 3D P25-graphene hydrogels were investigated [106,107]. removal = 98%,
BOD5 removal
= 94.2%, and dye
7. AOP compared to other treatment processes
removals = 99.9%
3 purified laccase of Acid blue 25 When free laccase is [110]
Numerous water treatment processes are currently in use and/or in Paraconiothyrium and acid used, decolourisation
the laboratory or pilot plant research stage. Every process has proven to variabile – free and orange 7 efficiency of Acid
be effective towards countless varieties of wastewater from a great deal immobilized on Blue 25 = 39% and
porous silica beads Acid Orange
of diverse sources. Table 5 has been listed few important processes dye removal 7 = 35% at
which can compare the treatment process that has high attention in the incubation time
research field [108–114]. = 65 min. When
All the oxidants, which have high oxidation potentials and their non- immobilized laccase
is used,
selective nature, fastest oxidation rates of OH molecules in treating the
decolourisation
wastewater makes the AOP on advantages over other treatment pro efficiency of Acid
cesses. In extension, mostly the organic materials within the wastewater Blue = 76% and Acid
convert into stable inorganic compounds in this AOP processes. The Orange 7 = 64% at
stable inorganic compounds such as salts, CO2 and water have formed incubation time
= 65 min
and this reduced to harmless compounds in treated effluents. The for 4 HPEI-Modified Reactive Blue Maximum dye [111]
mation of bromate and excess peroxides in the treated water can be is Fe3O4 (Fe@HPEI) 19 dye removal efficiency
sues but the well-designed AOP system can dealt the problems. This may Nanoparticle as a = 99.3% at
lead a high capital investment and maintenance cost for the operation. Superadsorbent for adsorption time
dye removal = 25 min; pH = 3.4;
Also, higher energy requirement, complex chemical mechanism and
initial nanoparticle
higher operating cost using chemical reagent are the significant prob dose = 0.4 g/L and
lems that has to be addressed in the implementation of the AOP. In dye loading
addition, utilizing peroxides should be based on controlled for residual = 113 mg/L. The
compounds. These residual peroxides might have potential negative maximum adsorption
capacity of Fe@HPEI
effects on treatment process and any associated consequences.
nanoparticles was
found to be 500 mg
8. Toxicity of nanoparticles dye per g absorbent.
5 Coagulation using Direct Red 23 Dye removal [112]
Moringa stenopetala azo dye efficiency was 99.2%
Nanoparticles are being used in various fields and it is dominating
coagulant (MSC) at optimum
the world of material science gradually due to their unusual and extreme conditions of pH 7,
properties but at the same time it is found to be toxic for various living MSC dose of 240 mg/
organisms when unintentionally released into the environment or L and an initial Direct
recycled. After using the nanoparticles in water treatment, the nano Red 23 azo dye
concentration of
particles are recoverable only to a certain extent. The irrecoverable 25 mg/L
nanoparticles are sent with the effluent but in small amounts but even in
these small quantities it can drastically affect the marine/aquatic life
and plants when the treated water is allowed to be reused or released
12
Table 5 (continued ) 8.1. Toxicity of metals and metallic oxide nanoparticles

S.no Method of treatment Compound (s) Remarks Ref
In case of metal and metal oxide nanoparticles, the exposure is sig
6 Enzymatic treatment Acid orange 7 In presence of pure [113]
using pure and low (AO7) HRP, color removal
nificant at concentrations > 0.5 μg/mL. The entry of these particles in
purity horseradish efficiency = 89% at the blood stream can cause cell damage and alter proteins expression of
peroxidase (HRP) 1 U/mL. In presence blood–brain barrier[115]. There are evidences of cytotoxicity in various
of low-purity HRP, sample cells and one such case is found in hamster ovary cells due to the
color removal
toxic effects of titanium oxide and aluminum oxide nanoparticles. The
efficiency = 73%.
The removal toxic effects are observed after an exposure time of 24 h. Genotoxic ef
efficiency was fects has also reported at concentrations > 0.5 μg/mL [116]. In case of
affected due to the titanium oxide the effects are insignificant when the DNA samples are
impurities present in incubated in the dark due to the well known photochemical properties of
the impure HRP.
7 Hybrid process – Crystal violet When only [114]
titanium oxide. But when the DNA samples are exposed to titanium
Hydrodynamic cavitation (CV) cavitation was oxide activated by either visible light or UVA light for about 30 mins
and adsorption on TiO2 done the TOC there is a very significant spike in the oxidative damage on the DNA
loaded polyacrilamide removal was sample [117]. In case of iron oxide nanoparticles, the risk of inhalation is
gel (PAM-TiO2) 19% and when
high and cell damage is found to occur after an exposure time of 12–24 h
only adsorption
was done the and at a concentration of 25–100 μg/mL. The cell damages can include
TOC removal low cell viability, apoptosis due to oxidative cell damage and also the
was 26% with blood clotting system is impacted [118]. The toxic effects of metals and
optimal metallic oxide nanoparticles have been represented in Fig. 3.
TiO2loading of
0.05 wt% but the
hybrid system
showed 73.6% 8.2. Toxicity of carbon and carbonaceous nanoparticles
TOC removal.
The duration was Fullerenes and its derivatives with surface modifications can be
fixed at a
constant
observed to provide significant cell damage including apoptosis and
90 mins. The decrease in proliferation of macrophage cells at relatively higher con
optimal centrations (> 100 μg/mL) at an exposure time of > 24 h [119]. In the
conditions were case of CNTs, they are the least biodegradable nanoparticles and prac
500 mg/L initial
tically insoluble in water but they are lipophilic in nature and therefore
concentration of
CV dye and 3 bar exposure of CNTs can result in permanent accumulation in the food
inlet pressure in chain and even exposure in organisms placed in the lowest of the food
the cavitation chain can reach human beings quickly, thus proving indirectly toxic for
equipment every organisms whether exposed or not [120]. The risks of accumula
tion of CNTs in the food chain were proven by the presence of SWCNTs
outside the textile industries thus posing a huge threat to the environ (single walled carbon nanotubes) in the digestive system of a suspension
ment. If the nanoparticles are lipophilic in nature, it will tend to stay in feeding worm, Caenorbabditis elegans. The CNTs are also very acces
the food chain ultimately ending up in our digestive system and thus sible for marine organisms when a study revealed the presence of
posing an indirect threat to human beings. So with the broad applica SWCNTs in the fecal matter of an exposed fish. It might’ve been
tions of the nanoparticles given above we have also included their consumed by the fish mistaking it for food. The risk of food chain
negative impacts on the environment. accumulation is also higher when the CNTs are consumed by benthi
vores [121]. The CNPs preparation involves processing in liquid medium
thus increasing the risk of dermal, oral and respiratory ingestion of the
CNPs in the manufacturers [122]. Skin penetration was major risk while
Fig. 3. Toxicity of metal and metal oxide nanoparticles.
13
Fig. 4. Toxicity of carbon and carbonaceous nanoparticles.
in contact with quantum dots. MWCNTs (multi-walled carbon nano writing—review and editing. S. S. Prakadeesh Raj: writing—review
tubes) were found to cause inflammation, apoptosis and human skin and editing. These authors contributed equally to this work.
fibroblasts [123–125]. Some vegetable plant seeds when are exposed to
aqueous suspensions of graphene oxides (500–2000 mg/L) were found Data Availability
to cause growth inhibition in the plants [126]. The toxic effects of car
bon and carbonaceous nanoparticles have been made clear with Fig. 4. No data was used for the research described in the article.
9. Conclusion Acknowledgement
This review provides the perspective and recent advancements of the The authors thank the SEED Grant Research Scheme (KSRCT/R&D/
catalytic AOPs in textile wastewater treatment, with focus on the for FT/2022), KSREI Trust. Also, The authors thank the KSREI Trust, Thir
mation and activation mechanisms of hydroxyl and sulphate radicals, uchengode for technical support.
along with the effect of using nanoparticle-based oxidation catalysts. In
general, the decomposition of water molecules into free radicals (via
radiation, photolysis, sonolysis or cavitation) which can eventually Consent to participate
attack the recalcitrant pollutant molecules, is of primary importance.
Although Fenton-based processes have been adapted towards economic All the authors who are involved in this review article show an
viability, there are still controversial issues related to the pollutants immense response for the article.
degradation and dissociation mechanisms. Novel catalytic oxidation
approaches with active radical agents can lead to enhanced degradation
Consent to publish
efficiency of the organic pollutants and to important development of
AOPs. To this end, the quantitative and qualitative analysis of the rad
All authors are harmoniously accepted their concern for publish this
icals formed may contribute to better understanding of the catalytic
review article.
oxidation processes. In summary, selective catalytic oxidation need to be
further developed towards efficient treatment of dye wastewaters for
their potential reuse in irrigation or back to the textile industry. Conflicts of interest statement
Ethical approval The authors whose names are listed immediately below certify that
they have NO affiliations with or involvement in any organization or
Not applicable. entity with any financial interest (such as honoraria; educational grants;
participation in speakers’ bureaus; membership, employment, consul
CRediT authorship contribution statement tancies, stock ownership, or other equity interest; and expert testimony
or patent-licensing arrangements), or non-financial interest (such as
R. Mahadevan: Conceptualization, writing— original draft and personal or professional relationships, affiliations, knowledge or beliefs)
editing. S. Palanisamy: supervision, funding acquisition and in the subject matter or materials discussed in this manuscript.
14
Disclosure statement [21] C. Santhosh, V. Velmurugan, G. Jacob, S.K. Jeong, A.N. Grace, A. Bhatnagar, Role
of nanomaterials in water treatment applications: A Review, Chem. Eng. J. 306
(2016) 1116–1137, https://doi.org/10.1016/j.cej.2016.08.053.
No potential conflict of interest was reported by the authors. Survey [22] Y. Shang, M.K. Hasan, G.J. Ahammed, M. Li, H. Yin, J. Zhou, Applications of
data are provided in full in the main section of this paper. nanotechnology in plant growth and Crop Protection: A Review, Molecules 24
(14) (2019) 2558, https://doi.org/10.3390/molecules24142558.
[23] M. Kumar, S. Ambika, A. Hassani, P.V. Nidheesh, Waste to catalyst:role of
References agricultural waste in water and wastewater treatment, Sci. Total Environ. 858
(2023), 159762, https://doi.org/10.1016/j.scitotenv.2022.159762.
[1] J. Guo, C. Lin, C. Jiang, P. Zhang, Review on noble metal-based catalysts for [24] A. Hassani, J. Scaria, F. Ghanbari, P.V. Nidheesh, Sulfate radicals-based advanced
formaldehyde oxidation at room temperature, Appl. Surf. Sci. 475 (2019) oxidation processes for the degradation of pharmaceuticals and personal care
237–255, https://doi.org/10.1016/j.apsusc.2018.12.238. products: a review on relevant activation mechanisms, performance, and
[2] W. Zhao, I.-W. Chen, F. Huang, Toward large-scale water treatment using perspectives, Environ. Res. 217 (2023), 114789, https://doi.org/10.1016/j.
nanomaterials, Nano Today 27 (2019) 11–27, https://doi.org/10.1016/j. envres.2022.114789.
nantod.2019.05.003. [25] A.V. Karim, A. Hassani, P. Eghbali, P.V. Nidheesh, Nanostructured modified
[3] S. Madihi-Bidgoli, S. Asadnezhad, A. Yaghoot-Nezhad, A. Hassani, Azurobine layered double hydroxides (1-DHS)-based catalysts: A review on synthesis,
degradation using Fe2O3@multi-walled carbon nanotube activated characterization, and applications in water remediation by advanced oxidation
peroxymonosulfate (PMS) under Uva-led irradiation: Performance, Mechanism processes, Curr. Opin. Solid State Mater. Sci. 26 (1) (2022), 100965, https://doi.
and Environmental Application, J. Environ. Chem. Eng. 9 (6) (2021), 106660, org/10.1016/j.cossms.2021.100965.
https://doi.org/10.1016/j.jece.2021.106660. [26] A. Hassani, M. Faraji, P. Eghbali, Facile fabrication of MPG-C3N4/Ag/ZnO
[4] A. Khataee, P. Eghbali, M.H. Irani-Nezhad, A. Hassani, Sonochemical synthesis of nanowires/zn photocatalyst plates for photodegradation of Dye Pollutant,
WS2 nanosheets and its application in sonocatalytic removal of organic dyes from J. Photochem. Photobiol. A: Chem. 400 (2020), 112665, https://doi.org/
water solution, Ultrason. Sonochem. 48 (2018) 329–339, https://doi.org/ 10.1016/j.jphotochem.2020.112665.
10.1016/j.ultsonch.2018.06.003. [27] I. Khan, K. Saeed, I. Khan, Nanoparticles: properties, applications and toxicities,
[5] C. Liu, S.L. Nauert, M.A. Alsina, D. Wang, A. Grant, K. He, E. Weitz, M. Nolan, K. Arab. J. Chem. 12 (7) (2019) 908–931, https://doi.org/10.1016/j.
A. Gray, J.M. Notestein, Role of surface reconstruction on Cu/TiO2 nanotubes for arabjc.2017.05.011.
CO2 Conversion, Appl. Catal. B: Environ. 255 (2019), 117754, https://doi.org/ [28] J.L. Wang, L.J. Xu, Advanced oxidation processes for wastewater treatment:
10.1016/j.apcatb.2019.117754. formation of hydroxyl radical and application, Crit. Rev. Environ. Sci. Technol. 42
[6] A.V. Karim, A. Hassani, P. Eghbali, P.V. Nidheesh, Nanostructured modified (3) (2012) 251–325, https://doi.org/10.1080/10643389.2010.507698.
layered double hydroxides (l-DHS)-based catalysts: A review on synthesis, [29] S.J. Mazivila, I.A. Ricardo, J.M.M. Leitão, J.C.G. Esteves da Silva, A review on
characterization, and applications in water remediation by advanced oxidation advanced oxidation processes: from classical to new perspectives coupled to two-
processes, Curr. Opin. Solid State Mater. Sci. 26 (1) (2022), 100965, https://doi. and multi-way calibration strategies to monitor degradation of contaminants in
org/10.1016/j.cossms.2021.100965. environmental samples, Trends Environ. Anal. Chem. 24 (2019), https://doi.org/
[7] T.H. Bokhari, N. Ahmad, M.I. Jilani, M. Saeed, M. Usman, A.U. Haq, R. Rehman, 10.1016/j.teac.2019.e00072.
M. Iqbal, A. Nazir, T. Javed, UV/ H2O2, UV/H2O2/SnO2 and Fe/H2O2 based [30] R. Dewil, D. Mantzavinos, I. Poulios, M.A. Rodrigo, New perspectives for
advanced oxidation processes for the degradation of disperse violet 63 in aqueous advanced oxidation processes, J. Environ. Manag. 195 (2017) 93–99, https://doi.
medium, Mater. Res. Express 7 (1) (2020), 015531, https://doi.org/10.1088/ org/10.1016/j.jenvman.2017.04.010.
2053-1591/ab6c15. [31] R. Bharati, S. Suresh, Biosynthesis of Zno/SiO2 nanocatalyst with Palash leaves’
[8] A. Baiju, R. Gandhimathi, S.T. Ramesh, P.V. Nidheesh, Combined heterogeneous powder for treatment of petroleum refinery effluent, Resour. -Effic. Technol. 3 (4)
electro-fenton and biological process for the treatment of stabilized landfill (2017) 528–541, https://doi.org/10.1016/j.reffit.2017.08.004.
leachate, J. Environ. Manag. 210 (2018) 328–337, https://doi.org/10.1016/j. [32] M. Sajjadi, N.Y. Baran, T. Baran, M. Nasrollahzadeh, M.R. Tahsili,
jenvman.2018.01.019. M. Shokouhimehr, Palladium nanoparticles stabilized on a novel Schiff base
[9] M.-hui Zhang, H. Dong, L. Zhao, D.-xi Wang, D. Meng, A review on Fenton modified Unye bentonite: highly stable, reusable and efficient nanocatalyst for
process for organic wastewater treatment based on optimization perspective, Sci. treating wastewater contaminants and inactivating pathogenic microbes, Sep.
Total Environ. 670 (2019) 110–121, https://doi.org/10.1016/j. Purif. Technol. 237 (2020), 116383, https://doi.org/10.1016/j.
scitotenv.2019.03.180. seppur.2019.116383.
[10] S. Venkatesh, K. Venkatesh, A.R. Quaff, Dye decomposition by combined [33] Anushree, S. Kumar, C. Sharma, Synthesis, characterization and application of
ozonation and anaerobic treatment: Cost effective technology, J. Appl. Res. CuO CEO2 nanocatalysts in wet air oxidation of industrial wastewater, J. Environ.
Technol. 15 (4) (2017) 340–345, https://doi.org/10.1016/j.jart.2017.02.006. Chem. Eng. 5 (4) (2017) 3914–3921, https://doi.org/10.1016/j.
[11] F. Deng, S. Qiu, C. Chen, X. Ding, F. Ma, Heterogeneous catalytic ozonation of jece.2017.07.061.
refinery wastewater over alumina-supported Mn and Cu oxides catalyst, Ozone.: [34] A.S. Adekunle, J.A.O. Oyekunle, L.M. Durosinmi, O.S. Oluwafemi, D.S. Olayanju,
Sci. Eng. 37 (6) (2015) 546–555, https://doi.org/10.1080/ A.S. Akinola, O.R. Obisesan, O.F. Akinyele, T.A. Ajayeoba, Potential of cobalt and
01919512.2015.1065173. cobalt oxide nanoparticles as nanocatalyst towards dyes degradation in
[12] K. Yong, J. Wu, S. Andrews, Heterogeneous catalytic ozonation of aqueous wastewater, Nano-Struct. Nano-Objects 21 (2020), 100405, https://doi.org/
reactive dye, Ozone.: Sci. Eng. 27 (4) (2005) 257–263, https://doi.org/10.1080/ 10.1016/j.nanoso.2019.100405.
01919510591005888. [35] A.S. Ethiraj, P. Uttam, V. K, K.F. Chong, G.A.M. Ali, Photocatalytic performance
[13] P.R. Gogate, A.B. Pandit, A review of imperative technologies for wastewater of a novel semiconductor nanocatalyst: Copper doped nickel oxide for phenol
treatment I: oxidation technologies at ambient conditions, Adv. Environ. Res. 8 degradation, Mater. Chem. Phys. 242 (2020), 122520, https://doi.org/10.1016/j.
(3–4) (2004) 501–551, https://doi.org/10.1016/s1093-0191(03)00032-7. matchemphys.2019.122520.
[14] U.I. Gaya, A.H. Abdullah, Heterogeneous photocatalytic degradation of organic [36] M. Parvas, M. Haghighi, S. Allahyari, Catalytic wet air oxidation of phenol over
contaminants over titanium dioxide: a review of Fundamentals, progress and ultrasound-assisted synthesized NI/CEO2–zro2 nanocatalyst used in wastewater
Problems, J. Photochem. Photobiol. C: Photochem. Rev. 9 (1) (2008) 1–12, treatment, Arab. J. Chem. 12 (7) (2019) 1298–1307, https://doi.org/10.1016/j.
https://doi.org/10.1016/j.jphotochemrev.2007.12.003. arabjc.2014.10.043.
[15] A. Hassani, J. Scaria, F. Ghanbari, P.V. Nidheesh, Sulfate radicals-based advanced [37] M. Moradi, M. Haghighi, S. Allahyari, Precipitation dispersion of ag–zno
oxidation processes for the degradation of pharmaceuticals and personal care nanocatalyst over functionalized multiwall carbon nanotube used in degradation
products: a review on relevant activation mechanisms, performance, and of acid orange from wastewater, Process Saf. Environ. Prot. 107 (2017) 414–427,
perspectives, Environ. Res. 217 (2023), 114789, https://doi.org/10.1016/j. https://doi.org/10.1016/j.psep.2017.03.010.
envres.2022.114789. [38] M.A. Mekewi, A.S. Darwish, Elaboration of metal (M: Co, Cu, ni, Fe) embedded
[16] Z. Eren, Ultrasound as a basic and auxiliary process for dye remediation: a review, poly(acrylic acid-co-acrylamide) hydrogel nanocomposites: An attempt to
J. Environ. Manag. 104 (2012) 127–141, https://doi.org/10.1016/j. synthesize uncommon architectured “auto-active” nanocatalysts for treatment of
jenvman.2012.03.028. dyeing wastewater, Mater. Res. Bull. 70 (2015) 607–620, https://doi.org/
[17] E.G. Garrido-Ramírez, B.K.G. Theng, M.L. Mora, Clays and oxide minerals as 10.1016/j.materresbull.2015.05.035.
catalysts and nanocatalysts in Fenton-like reactions — a review, Appl. Clay Sci. [39] M.S. Najafinejad, P. Mohammadi, M. Mehdi Afsahi, H. Sheibani, Biosynthesis of
47 (3–4) (2010) 182–192, https://doi.org/10.1016/j.clay.2009.11.044. au nanoparticles supported on fe3o4@polyaniline as a heterogeneous and
[18] A. Fernandes, M.J. Pacheco, L. Ciríaco, A. Lopes, Review on the electrochemical reusable magnetic nanocatalyst for reduction of the azo dyes at ambient
processes for the treatment of sanitary landfill leachates: Present and future, Appl. temperature, Mater. Sci. Eng.: C. 98 (2019) 19–29, https://doi.org/10.1016/j.
Catal. B: Environ. 176–177 (2015) 183–200, https://doi.org/10.1016/j. msec.2018.12.098.
apcatb.2015.03.052. [40] M. Rostamizadeh, A. Jafarizad, S. Gharibian, High efficient decolorization of
[19] A. Buthiyappan, A.R. Abdul Aziz, W.M. Wan Daud, Recent advances and reactive red 120 azo dye over reusable Fe-ZSM-5 nanocatalyst in Electro-Fenton
prospects of catalytic advanced oxidation process in treating textile effluents, reaction, Sep. Purif. Technol. 192 (2018) 340–347, https://doi.org/10.1016/j.
Rev. Chem. Eng. 32 (1) (2016) 1–47, https://doi.org/10.1515/revce-2015-0034. seppur.2017.10.041.
[20] M. Anjum, R. Miandad, M. Waqas, F. Gehany, M.A. Barakat, Remediation of [41] L. Khaledi Maki, A. Maleki, R. Rezaee, H. Daraei, K. Yetilmezsoy, LED-activated
wastewater using various nano-materials, Arab. J. Chem. 12 (8) (2019) immobilized Fe-Ce-n tri-doped Tio2 nanocatalyst on glass bed for photocatalytic
4897–4919, https://doi.org/10.1016/j.arabjc.2016.10.004. degradation organic dye from aqueous solutions, Environ. Technol. Innov. 15
(2019), 100411, https://doi.org/10.1016/j.eti.2019.100411.
15
[42] Y. Wang, L. He, Y. Li, L. Jing, J. Wang, X. Li, AG NPS supported on the magnetic [66] L. Bergamonti, C. Bergonzi, C. Graiff, P.P. Lottici, R. Bettini, L. Elviri, 3D printed
al-mof/PDA as nanocatalyst for the removal of organic pollutants in water, chitosan scaffolds: a new TiO2 support for the photocatalytic degradation of
J. Alloy. Compd. 828 (2020), 154340, https://doi.org/10.1016/j. amoxicillin in water, Water Res. 163 (2019), 114841, https://doi.org/10.1016/j.
jallcom.2020.154340. watres.2019.07.008.
[43] J. Feng, R.S.K. Wong, X. Hu, P.L. Yue, Discoloration and mineralization of orange [67] T. Olmez-Hanci, I. Arslan-Alaton, Comparison of sulfate and hydroxyl radical
II by using fe3+-doped tio2 and bentonite clay-based Fe nanocatalysts, Catal. based advanced oxidation of phenol, Chem. Eng. J. 224 (2013) 10–16, https://
Today 98 (3) (2004) 441–446, https://doi.org/10.1016/j.cattod.2004.08.007. doi.org/10.1016/j.cej.2012.11.007.
[44] G.R.S. Andrade, C.C. Nascimento, E.C. Silva Júnior, D.T.S.L. Mendes, I. [68] H. Wu, X. Xu, L. Shi, Y. Yin, L.-C. Zhang, Z. Wu, X. Duan, S. Wang, H. Sun,
F. Gimenez, ZnO/AU nanocatalysts for enhanced decolorization of an azo dye Manganese oxide integrated catalytic ceramic membrane for degradation of
under solar, UV-A and dark conditions, J. Alloy. Compd. 710 (2017) 557–566, organic pollutants using sulfate radicals, Water Res. 167 (2019), 115110, https://
https://doi.org/10.1016/j.jallcom.2017.03.295. doi.org/10.1016/j.watres.2019.115110.
[45] H. Veisi, S. Razeghi, P. Mohammadi, S. Hemmati, Silver nanoparticles decorated [69] Z. Wang, V. Srivastava, I. Ambat, Z. Safaei, M. Sillanpää, Degradation of
on thiol-modified magnetite nanoparticles (fe3o4/sio2-pr-S-AG) as a recyclable ibuprofen by UV-led/catalytic advanced oxidation process, J. Water Process Eng.
nanocatalyst for degradation of organic dyes, Mater. Sci. Eng.: C. 97 (2019) 31 (2019), 100808, https://doi.org/10.1016/j.jwpe.2019.100808.
624–631, https://doi.org/10.1016/j.msec.2018.12.076. [70] Z. Liu, S. Yang, Y. Yuan, J. Xu, Y. Zhu, J. Li, F. Wu, A novel heterogeneous system
[46] F. Han, V.S.R. Kambala, R. Dharmarajan, Y. Liu, R. Naidu, Photocatalytic for sulfate radical generation through sulfite activation on a CoFe2O4
degradation of azo dye acid orange 7 using different light sources over fe3+- nanocatalyst surface, J. Hazard. Mater. 324 (2017) 583–592, https://doi.org/
doped tio2 nanocatalysts, Environ. Technol. Innov. 12 (2018) 27–42, https://doi. 10.1016/j.jhazmat.2016.11.029.
org/10.1016/j.eti.2018.07.004. [71] S.-M. Hao, M.-Y. Yu, Y.-J. Zhang, Y. Abdelkrim, J. Qu, Hierarchical mesoporous
[47] S. Sajjadi, A. Khataee, M. Kamali, Sonocatalytic degradation of methylene blue by cobalt silicate architectures as high-performance sulfate-radical-based advanced
a novel graphene quantum dots anchored CdSe nanocatalyst, Ultrason. oxidization catalysts, J. Colloid Interface Sci. 545 (2019) 128–137, https://doi.
Sonochem. 39 (2017) 676–685, https://doi.org/10.1016/j.ultsonch.2017.05.030. org/10.1016/j.jcis.2019.03.017.
[48] S.D. Pattisson, From support to carbocatalyst: The aerobic and solvent free [72] Q. Ni, J. Ma, C. Fan, Y. Kong, M. Peng, S. Komarneni, Spinel-type cobalt-
epoxidation of Dec-1-ene using graphitic oxide as a catalyst (thesis), Cardiff manganese oxide catalyst for degradation of Orange II using a novel
University,, 2017. heterogeneous photo-chemical catalysis system, Ceram. Int. 44 (16) (2018)
[49] Z. Zhang, F. Xiao, Y. Guo, S. Wang, Y. Liu, One-pot self-assembled three- 19474–19480, https://doi.org/10.1016/j.ceramint.2018.07.184.
dimensional tio2-graphene hydrogel with improved adsorption capacities and [73] D. Coello-Fiallos, E. Cazzanelli, A. Tavolaro, P. Tavolaro, M. Arias, L.S. Caputi,
photocatalytic and electrochemical activities, ACS Appl. Mater. Interfaces 5 (6) Cresyl violet adsorption on sonicated graphite oxide, J. Nanosci. Nanotechnol. 18
(2013) 2227–2233, https://doi.org/10.1021/am303299r. (4) (2018) 3006–3011, https://doi.org/10.1166/jnn.2018.14337.
[50] A. Šuligoj, A. Ristić, G. Dražić, A. Pintar, N.Z. Logar, N.N. Tušar, Bimetal cu-Mn [74] Z. Zhang, F. Xiao, Y. Guo, S. Wang, Y. Liu, One-pot self-assembled three-
porous silica-supported catalyst for Fenton-like degradation of organic dyes in dimensional tio2-graphene hydrogel with improved adsorption capacities and
wastewater at neutral ph, Catal. Today 358 (2020) 270–277, https://doi.org/ photocatalytic and electrochemical activities, ACS Appl. Mater. Interfaces 5 (6)
10.1016/j.cattod.2020.03.047. (2013) 2227–2233, https://doi.org/10.1021/am303299r.
[51] N.N. Tušar, D. Maučec, M. Rangus, I. Arčon, M. Mazaj, M. Cotman, A. Pintar, [75] P. Hu, M. Long, Cobalt-catalyzed sulfate radical-based advanced oxidation: a
V. Kaučič, Manganese functionalized silicate nanoparticles as a Fenton-type review on heterogeneous catalysts and applications, Appl. Catal. B: Environ. 181
catalyst for water purification by advanced oxidation processes (AOP), Adv. (2016) 103–117, https://doi.org/10.1016/j.apcatb.2015.07.024.
Funct. Mater. 22 (4) (2011) 820–826, https://doi.org/10.1002/adfm.201102361. [76] L. Hou, X. Li, Q. Yang, F. Chen, S. Wang, Y. Ma, Y. Wu, X. Zhu, X. Huang,
[52] X. Qin, D. Shi, B. Guo, C. Fu, J. Zhang, Q. Xie, X. Shi, F. Chen, X. Qin, W. Yu, D. Wang, Heterogeneous activation of peroxymonosulfate using MN-FE layered
X. Feng, Y. Liu, D. Luo, Anion-regulated synthesis of zno 1D necklace-like double hydroxide: Performance and mechanism for organic pollutant
nanostructures with high photocatalytic activity, Nanoscale Res. Lett. 15 (1) degradation, Sci. Total Environ. 663 (2019) 453–464, https://doi.org/10.1016/j.
(2020), https://doi.org/10.1186/s11671-020-03435-5. scitotenv.2019.01.190.
[53] A.P. Naik, A.V. Salkar, M.S. Majik, P.P. Morajkar, Enhanced photocatalytic [77] L. Hu, G. Deng, W. Lu, Y. Lu, Y. Zhang, Peroxymonosulfate activation by MN 3 O
degradation of amaranth dye on mesoporous anatase tio2: evidence of C–N, N– –N 4 /metal-organic framework for degradation of refractory aqueous organic
bond cleavage and identification of new intermediates, Photochem. Photobiol. pollutant rhodamine B, Chin. J. Catal. 38 (8) (2017) 1360–1372, https://doi.org/
Sci. 16 (7) (2017) 1126–1138, https://doi.org/10.1039/c7pp00090a. 10.1016/s1872-2067(17)62875-4.
[54] S. Bagheri, N. Muhd Julkapli, S. Bee Abd Hamid, Titanium dioxide as a catalyst [78] J. Li, P. Ye, J. Fang, M. Wang, D. Wu, A. Xu, X. Li, Peroxymonosulfate activation
support in heterogeneous catalysis, Sci. World J. 2014 (2014) 1–21, https://doi. and pollutants degradation over highly dispersed cuo in manganese oxide
org/10.1155/2014/727496. octahedral molecular sieve, Appl. Surf. Sci. 422 (2017) 754–762, https://doi.org/
[55] B. Ozbey Unal, Z. Bilici, N. Ugur, Z. Isik, E. Harputlu, N. Dizge, K. Ocakoglu, 10.1016/j.apsusc.2017.06.118.
Adsorption and Fenton oxidation of azo dyes by magnetite nanoparticles [79] C. Liu, D. Pan, X. Tang, M. Hou, Q. Zhou, J. Zhou, Degradation of rhodamine B by
deposited on a glass substrate, J. Water Process Eng. 32 (2019), 100897, https:// the α-mno2/peroxymonosulfate system, Water, Air, Soil Pollut. 227 (3) (2016),
doi.org/10.1016/j.jwpe.2019.100897. https://doi.org/10.1007/s11270-016-2782-6.
[56] S. J.L. Duarte da, L. Meili, L. de M. Gomes, J.I. Soletti, P. e S. C.L.Zanta de, [80] Q. Ma, X. Zhang, R. Guo, H. Zhang, Q. Cheng, M. Xie, X. Cheng, Persulfate
Electrochemical process and Fenton reaction followed by lamellar settler to oil/ activation by magnetic γ-FE2O3/MN3O4 nanocomposites for degradation of
surfactant effluent degradation, J. Water Process Eng. 31 (2019), 100841, organic pollutants, Sep. Purif. Technol. 210 (2019) 335–342, https://doi.org/
https://doi.org/10.1016/j.jwpe.2019.100841. 10.1016/j.seppur.2018.06.060.
[57] Y.-G. Kang, H. Yoon, C.-S. Lee, E.-J. Kim, Y.-S. Chang, Advanced oxidation and [81] X. Tang, J. Huang, K. Liu, Q. Feng, Z. Li, M. Ao, Synthesis of magnetically
adsorptive bubble separation of dyes using MnO2-coated fe3o4 nanocomposite, separable MNO2/FE3O4/silica nanofiber composite with enhanced Fenton-like
Water Res. 151 (2019) 413–422, https://doi.org/10.1016/j.watres.2018.12.038. catalytic activity for degradation of acid red 73, Surf. Coat. Technol. 354 (2018)
[58] D. Yuan, C. Zhang, S. Tang, X. Li, J. Tang, Y. Rao, Z. Wang, Q. Zhang, Enhancing 18–27, https://doi.org/10.1016/j.surfcoat.2018.09.011.
CaO2 Fenton-like process by Fe(ii)-oxalic acid complexation for organic [82] M. Wang, Y. Wei, Q. Zou, W. Zhang, A. Xu, X. Li, Tuning manganese (III) species
wastewater treatment, Water Res. 163 (2019), 114861, https://doi.org/10.1016/ in manganese oxide octahedral molecular sieve by interaction with carbon
j.watres.2019.114861. nanofibers for enhanced pollutant degradation in the presence of
[59] C.R. Holkar, A.J. Jadhav, D.V. Pinjari, N.M. Mahamuni, A.B. Pandit, A critical peroxymonosulfate, J. Colloid Interface Sci. 536 (2019) 271–280, https://doi.
review on textile wastewater treatments: Possible approaches, J. Environ. Manag. org/10.1016/j.jcis.2018.10.055.
182 (2016) 351–366, https://doi.org/10.1016/j.jenvman.2016.07.090. [83] Y. Xu, H. Lin, Y. Li, H. Zhang, The mechanism and efficiency of MNO2 activated
[60] A.A. Taha, L. Huang, S. Ramakrishna, Y. Liu, MOF [NH2-mil-101(Fe)] as a persulfate process coupled with electrolysis, Sci. Total Environ. 609 (2017)
powerful and reusable Fenton-like catalyst, J. Water Process Eng. 33 (2020), 644–654, https://doi.org/10.1016/j.scitotenv.2017.07.151.
101004, https://doi.org/10.1016/j.jwpe.2019.101004. [84] X. Zhao, C. Niu, L. Zhang, H. Guo, X. Wen, C. Liang, G. Zeng, Co-mn layered
[61] W. Xiang, T. Zhou, Y. Wang, M. Huang, X. Wu, J. Mao, X. Lu, B. Zhang, Catalytic double hydroxide as an effective heterogeneous catalyst for degradation of
oxidation of diclofenac by hydroxylamine-enhanced cu nanoparticles and the organic dyes by activation of peroxymonosulfate, Chemosphere 204 (2018)
efficient neutral heterogeneous-homogeneous reactive copper cycle, Water Res. 11–21, https://doi.org/10.1016/j.chemosphere.2018.04.023.
153 (2019) 274–283, https://doi.org/10.1016/j.watres.2019.01.024. [85] X. Hao, X. Wang, R. Liu, S. Li, M.C.M. van Loosdrecht, H. Jiang, Environmental
[62] P.V. Nidheesh, J. Khatri, T.S. Anantha Singh, R. Gandhimathi, S.T. Ramesh, impacts of resource recovery from wastewater treatment plants, Water Res. 160
Review of zero-valent aluminium based water and wastewater treatment (2019) 268–277, https://doi.org/10.1016/j.watres.2019.05.068.
methods, Chemosphere 200 (2018) 621–631, https://doi.org/10.1016/j. [86] H. Wang, W. Guo, B. Liu, Q. Wu, H. Luo, Q. Zhao, Q. Si, F. Sseguya, N. Ren, Edge-
chemosphere.2018.02.155. nitrogenated biochar for efficient peroxydisulfate activation: An electron transfer
[63] X. Da, H. Ji, Z. Zhao, R. Lan, T. Li, J. Ma, Strongly prolonged hydroxyl radical mechanism, Water Res. 160 (2019) 405–414, https://doi.org/10.1016/j.
production for Fenton-like reactions: the golden touch of cu, Sep. Purif. Technol. watres.2019.05.059.
213 (2019) 500–506, https://doi.org/10.1016/j.seppur.2018.12.060. [87] W.-D. Oh, T.-T. Lim, Design and application of heterogeneous catalysts as
[64] R. Bhateria, R. Singh, A review on nanotechnological application of magnetic iron peroxydisulfate activator for organics removal: An overview, Chem. Eng. J. 358
oxides for heavy metal removal, J. Water Process Eng. 31 (2019), 100845, (2019) 110–133, https://doi.org/10.1016/j.cej.2018.09.203.
https://doi.org/10.1016/j.jwpe.2019.100845. [88] X. Chen, X. Qiao, D. Wang, J. Lin, J. Chen, Kinetics of oxidative decolorization
[65] S. Wacławek, H.V. Lutze, K. Grübel, V.V.T. Padil, M. Černík, D.D. Dionysiou, and mineralization of Acid Orange 7 by dark and photoassisted CO2+-catalyzed
Chemistry of persulfates in water and wastewater treatment: A Review, Chem. peroxymonosulfate system, Chemosphere 67 (4) (2007) 802–808, https://doi.
Eng. J. 330 (2017) 44–62, https://doi.org/10.1016/j.cej.2017.07.132. org/10.1016/j.chemosphere.2006.10.032.
16
[89] M. Suh, P.S. Bagus, S. Pak, M.P. Rosynek, J.H. Lunsford, Reactions of hydroxyl adsorption processes, Desalin. Water Treat. 57 (20) (2015) 9203–9215, https://
radicals on Titania, silica, alumina, and gold surfaces, J. Phys. Chem. B 104 (12) doi.org/10.1080/19443994.2015.1027960.
(2000) 2736–2742, https://doi.org/10.1021/jp993653e. [109] S.-S. Mirzadeh, S.-M. Khezri, S. Rezaei, H. Forootanfar, A.H. Mahvi, M.
[90] J. Huang, H. Zhang, MN-based catalysts for sulfate radical-based advanced A. Faramarzi, Decolorization of two synthetic dyes using the purified laccase of
oxidation processes: a review, Environ. Int. 133 (2019), 105141, https://doi.org/ paraconiothyrium variabile immobilized on porous silica beads, J. Environ.
10.1016/j.envint.2019.105141. Health Sci. Eng. 12 (1) (2014), https://doi.org/10.1186/2052-336x-12-6.
[91] Q. Ni, J. Ma, C. Fan, Y. Kong, M. Peng, S. Komarneni, Spinel-type cobalt- [110] A. Dalvand, M. Khoobi, R. Nabizadeh, M.R. Ganjali, E. Gholibegloo, A.H. Mahvi,
manganese oxide catalyst for degradation of Orange II using a novel Reactive dye adsorption from aqueous solution on HPEI-modified Fe3O4
heterogeneous photo-chemical catalysis system, Ceram. Int. 44 (16) (2018) nanoparticle as a superadsorbent: characterization, modeling, and optimization,
19474–19480, https://doi.org/10.1016/j.ceramint.2018.07.184. J. Polym. Environ. 26 (8) (2018) 3470–3483, https://doi.org/10.1007/s10924-
[92] J. Yu, L. Tang, Y. Pang, G. Zeng, J. Wang, Y. Deng, Y. Liu, H. Feng, S. Chen, 018-1231-6.
X. Ren, Magnetic nitrogen-doped sludge-derived biochar catalysts for persulfate [111] A. Dalvand, E. Gholibegloo, M.R. Ganjali, N. Golchinpoor, M. Khazaei, H. Kamani,
activation: Internal Electron Transfer Mechanism, Chem. Eng. J. 364 (2019) S.S. Hosseini, A.H. Mahvi, Comparison of moringa stenopetala seed extract as a
146–159, https://doi.org/10.1016/j.cej.2019.01.163. clean coagulant with alum and moringa stenopetala-alum hybrid coagulant to
[93] X. Chen, W.-D. Oh, T.-T. Lim, Graphene- and CNTS-based carbocatalysts in remove direct dye from textile wastewater, Environ. Sci. Pollut. Res. 23 (16)
persulfates activation: material design and catalytic mechanisms, Chem. Eng. J. (2016) 16396–16405, https://doi.org/10.1007/s11356-016-6708-z.
354 (2018) 941–976, https://doi.org/10.1016/j.cej.2018.08.049. [112] F. Gholami-Borujeni, A.H. Mahvi, S. Nasseri, M.A. Faramarzi, R. Nabizadeh,
[94] C. Han, X. Duan, M. Zhang, W. Fu, X. Duan, W. Ma, S. Liu, S. Wang, X. Zhou, Role M. Alimohammadi, Enzymatic treatment and detoxification of acid orange 7 from
of electronic properties in partition of radical and nonradical processes of textile wastewater, Appl. Biochem. Biotechnol. 165 (5–6) (2011) 1274–1284,
carbocatalysis toward peroxymonosulfate activation, Carbon 153 (2019) 73–80, https://doi.org/10.1007/s12010-011-9345-5.
https://doi.org/10.1016/j.carbon.2019.06.107. [113] A. Raj, B. Bethi, S.H. Sonawane, Investigation of removal of crystal violet dye
[95] P. Hu, M. Long, Cobalt-catalyzed sulfate radical-based advanced oxidation: a using novel hybrid technique involving hydrodynamic cavitation and hydrogel,
review on heterogeneous catalysts and applications, Appl. Catal. B: Environ. 181 J. Environ. Chem. Eng. 6 (4) (2018) 5311–5319, https://doi.org/10.1016/j.
(2016) 103–117, https://doi.org/10.1016/j.apcatb.2015.07.024. jece.2018.08.016.
[96] B.-C. Huang, J. Jiang, G.-X. Huang, H.-Q. Yu, Sludge biochar-based catalysts for [114] A.B. Sengul, E. Asmatulu, Toxicity of metal and metal oxide nanoparticles: a
improved pollutant degradation by activating peroxymonosulfate, J. Mater. review, Environ. Chem. Lett. 18 (5) (2020) 1659–1683, https://doi.org/10.1007/
Chem. A 6 (19) (2018) 8978–8985, https://doi.org/10.1039/c8ta02282h. s10311-020-01033-6.
[97] X. Xiao, B. Chen, Z. Chen, L. Zhu, J.L. Schnoor, Insight into multiple and [115] A.L. Di Virgilio, M. Reigosa, P.M. Arnal, M. Fernández Lorenzo de Mele,
multilevel structures of biochars and their potential environmental applications: Comparative study of the cytotoxic and genotoxic effects of titanium oxide and
A critical review, Environ. Sci. Technol. 52 (9) (2018) 5027–5047, https://doi. aluminium oxide nanoparticles in Chinese hamster ovary (Cho-K1) cells,
org/10.1021/acs.est.7b06487. J. Hazard. Mater. 177 (1–3) (2010) 711–718, https://doi.org/10.1016/j.
[98] J. Wang, Z. Liao, J. Ifthikar, L. Shi, Y. Du, J. Zhu, S. Xi, Z. Chen, Z. Chen, jhazmat.2009.12.089.
Treatment of refractory contaminants by sludge-derived biochar/persulfate [116] E.J. Petersen, V. Reipa, S.S. Watson, D.L. Stanley, S.A. Rabb, B.C. Nelson, DNA
system via both adsorption and advanced oxidation process, Chemosphere 185 damaging potential of photoactivated p25 titanium dioxide nanoparticles, Chem.
(2017) 754–763, https://doi.org/10.1016/j.chemosphere.2017.07.084. Res. Toxicol. 27 (10) (2014) 1877–1884, https://doi.org/10.1021/tx500340v.
[99] W. Tang, J. Liang, D. He, J. Gong, L. Tang, Z. Liu, D. Wang, G. Zeng, Various cell [117] K.X. Tan, A. Barhoum, S. Pan, M.K. Danquah, Risks and toxicity of nanoparticles
architectures of capacitive deionization: recent advances and future trends, Water and nanostructured materials, Emerg. Appl. Nanopart. Archit. Nanostruct. (2018)
Res. 150 (2019) 225–251, https://doi.org/10.1016/j.watres.2018.11.064. 121–139, https://doi.org/10.1016/b978-0-323-51254-1.00005-1.
[100] C. Nie, Z. Ao, X. Duan, C. Wang, S. Wang, T. An, Degradation of aniline by [118] K. Xiang, Z. Dou, Y. Li, Y. Xu, J. Zhu, S. Yang, H. Sun, Y. Liu, Cytotoxicity and
electrochemical activation of peroxydisulfate at MWCNT cathode: The proofed TNF-α secretion in raw264.7 macrophages exposed to different fullerene
concept of nonradical oxidation process, Chemosphere 206 (2018) 432–438, derivatives, J. Nanosci. Nanotechnol. 12 (3) (2012) 2169–2178, https://doi.org/
https://doi.org/10.1016/j.chemosphere.2018.04.173. 10.1166/jnn.2012.5681.
[101] C. Nie, Z. Dai, H. Meng, X. Duan, Y. Qin, Y. Zhou, Z. Ao, S. Wang, T. An, [119] Y. Wu, J.A.S. Hudson, Q. Lu, J.M. Moore, A.S. Mount, A.M. Rao, E. Alexov, P.
Peroxydisulfate activation by positively polarized carbocatalyst for enhanced C. Ke, Coating single-walled carbon nanotubes with phospholipids, J. Phys. Chem.
removal of aqueous organic pollutants, Water Res. 166 (2019), 115043, https:// B 110 (6) (2006) 2475–2478, https://doi.org/10.1021/jp057252c.
doi.org/10.1016/j.watres.2019.115043. [120] E. Oberdörster, S. Zhu, T.M. Blickley, P. McClellan-Green, M.L. Haasch,
[102] S. Singh, V. Kumar, R. Romero, K. Sharma, J. Singh, Applications of nanoparticles Ecotoxicology of carbon-based engineered nanoparticles: Effects of fullerene
in wastewater treatment, Nanobiotechnology Bioformulations (2019) 395–418, (C60) on Aquatic Organisms, Carbon 44 (6) (2006) 1112–1120, https://doi.org/
https://doi.org/10.1007/978-3-030-17061-5_17. 10.1016/j.carbon.2005.11.008.
[103] Y. Wang, C. Pan, W. Chu, A. Vipin, L. Sun, Environmental remediation [121] V.L. Colvin, Erratum: Corrigendum: The potential environmental impact of
applications of carbon nanotubes and graphene oxide: Adsorption and catalysis, engineered nanomaterials, 760–760, Nat. Biotechnol. 22 (6) (2004), https://doi.
Nanomaterials 9 (3) (2019) 439, https://doi.org/10.3390/nano9030439. org/10.1038/nbt0604-760c.
[104] K.S. Novoselov, E. McCann, S.V. Morozov, V.I. Fal’ko, M.I. Katsnelson, U. Zeitler, [122] R. Zhang, A.F. Khalizov, J. Pagels, D. Zhang, H. Xue, P.H. McMurry, Variability in
D. Jiang, F. Schedin, A.K. Geim, Unconventional Quantum Hall effect and Berry’s morphology, hygroscopicity, and optical properties of soot aerosols during
phase of 2π in bilayer graphene, Nat. Phys. 2 (3) (2006) 177–180, https://doi. atmospheric processing, Proc. Natl. Acad. Sci. 105 (30) (2008) 10291–10296,
org/10.1038/nphys245. https://doi.org/10.1073/pnas.0804860105.
[105] H. Hu, Y. Lin, Y.H. Hu, Core-shell structured TIO2 as highly efficient visible light [123] L. Zhang, W. Yu, V. Colvin, N. Monteiro-Riviere, Biological interactions of
photocatalyst for dye degradation, Catal. Today 341 (2020) 90–95, https://doi. quantum dot nanoparticles in skin and in human epidermal keratinocytes,
org/10.1016/j.cattod.2019.01.077. Toxicol. Appl. Pharmacol. 228 (2) (2008) 200–211, https://doi.org/10.1016/j.
[106] S. Luo, C. Liu, S. Zhou, W. Li, C. Ma, S. Liu, W. Yin, H.J. Heeres, W. Zheng, taap.2007.12.022.
K. Seshan, S. He, Zno nanorod arrays assembled on activated carbon fibers for [124] L. Ding, J. Stilwell, T. Zhang, O. Elboudwarej, H. Jiang, J.P. Selegue, P.A. Cooke,
photocatalytic degradation: Characteristics and synergistic effects, Chemosphere J.W. Gray, F.F. Chen, Molecular characterization of the cytotoxic mechanism of
261 (2020), 127731, https://doi.org/10.1016/j.chemosphere.2020.127731. multiwall carbon nanotubes and nano-onions on human skin fibroblast, Nano
[107] E. Bazrafshan, F.K. Mostafapour, A.R. Hosseini, A. Raksh Khorshid, A.H. Mahvi, Lett. 5 (12) (2005) 2448–2464, https://doi.org/10.1021/nl051748o.
Decolorisation of reactive red 120 dye by using single-walled carbon nanotubes in [125] M.A. Maurer-Jones, I.L. Gunsolus, C.J. Murphy, C.L. Haynes, Toxicity of
aqueous solutions, J. Chem. 2013 (2013) 1–8, https://doi.org/10.1155/2013/ engineered nanoparticles in the environment, Anal. Chem. 85 (6) (2013)
938374. 3036–3049, https://doi.org/10.1021/ac303636s.
[108] E. Bazrafshan, M.R. Alipour, A.H. Mahvi, Textile wastewater treatment by
application of combined chemical coagulation, electrocoagulation, and
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Sustainable Chemistry for the Environment 4 (2023) 100044

Contents lists available at ScienceDirect

Sustainable Chemistry for the Environment

Role of nanoparticles as oxidation catalyst in the treatment of textile

1. Introduction Textile industry is a major water polluting industry around many

detailed information on dye degradation using nanoparticles for 4. Nanoparticles

was 97.1% at high initial dye

hydrothermal dye concentration = 5 mg\L;

5.1.1. Titanium and Titanium Oxides (TiOx)

Fig. 1. Schematic diagram of H2O2 activation by the catalyst [59].

Co2+ + OH− → CoOH+ (Reaction 6) HSO−5 + Mn2O3 → SO•−

Co2+ + H2O → CoOH+ + H+ SO•−

CoO+ + 2 H+ → Co3+ + H2O 2HO•→ 1∕12O2+ HO

Moreover, studies on usage of MnOx other than MnO2 such as MnO,

6.1.2. Manganese catalyst HSO−5 + 2MnO → SO•− +

Fig. 2. Activation of PMS and PDS by Co in wastewater treatment mechanism [71].

able electrolysis of electrosorption process have proved as high energy

Table 5 (continued ) 8.1. Toxicity of metals and metallic oxide nanoparticles

Fig. 3. Toxicity of metal and metal oxide nanoparticles.

Fig. 4. Toxicity of carbon and carbonaceous nanoparticles.

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