Colloid and Interface Science Communications 37 (2020) 100281

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Colloid and Interface Science Communications

journal homepage: www.elsevier.com/locate/colcom

Synthesis of antibacterial, antioxidant and magnetic Nigella sativa-graphene T

oxide based nanocomposite BC-GO@Fe3O4 for water treatment
Nusrat Taraa, Sharf Ilahi Siddiquia, Ranjeet Kumar Niralab,c, Noufal Komby Abdullaa,
Saif Ali Chaudhrya,
⁎

a
Environmental Chemistry Research Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi 110025, India
b
Centre for Interdisciplinary Research in Basic Sciences, Jamia Millia Islamia, New Delhi 110025, India
c
National Institute of Health and Family Welfare, Munirka, New Delhi 110067, India

ARTICLE INFO ABSTRACT

Keywords: The multifunctional nanocomposite BC-GO@Fe3O4 was prepared by incorporating magnetic Fe3O4 nanoparticles
Graphene oxide in cellulosic Black cumin seed powder which was functionalized with graphene oxide following co-precipitation
Black cumin method. The prepared BC-GO@Fe3O4 was characterized by employing thermal, spectroscopic and microscopic
Fe3O4 techniques that showed high thermal stability, magnetic behaviour, and the presence of large numbers of hy-
Adsorption
droxyl and carbonyl functional groups at the surface. The in vitro investigation has shown that BC-GO@Fe3O4
Antibacterial
possesses significant antibacterial activities against Gram-negative and Gram-positive bacterial strains, and an-
Antioxidant
tioxidant capability. Thus the prepared nanocomposite is biologically safe and beneficial; therefore was tested
for adsorptive removal of both cationic and anionic representative water pollutants, namely, methylene blue and
arsenic from their aqueous solutions. The removal was carried out under variable conditions and the process has
been investigated thoroughly. The adsorption data for both methylene blue and arsenic fitted well to the
Freundlich isotherm and pseudo-second order kinetics which suggested that both these pollutants, during ad-
sorption, bound specifically to the chemically active sites on the surface of BC-GO@Fe3O4. However, for com-
parison purpose the Langmuir capacity was determined at equilibrium which was found to be approximately
10.0 mg g−1 for methylene blue and 1.0 mg g−1 for arsenic at optimum conditions (Adsorbent dose: 1.0 g L−1
for both methylene and arsenic; initial concentration: 10.0 and 1.0 mg L−1, and pH: 7.0 for methylene blue and
arsenic, respectively). The obtained adsorption capacities were compared with previously reported adsorption
capacities for various adsorbents for methylene blue and arsenic which proved the better adsorption capacities of
BC-GO@Fe3O4 for the present study. Therefore, BC-GO@Fe3O4, a biologically safe and beneficial material, can
be employed for adsorptive removal of dyes and arsenic from water while controlling the bacterial growth and
acting as antioxidant.

1. Introduction guideline value of 10 μg L−1 [3,4]. It has been estimated that about 140
million people living in 50 countries are drinking water containing
Arsenic, a highly notorious and toxic element, exists in combined arsenic more than WHO limit [3,5]. Another serious issue, related to
form with other elements and gets dissolved in water aquifer. The water pollution, is discharge of wastewater by the textile industries that
drinking of arsenic contaminated water causes adverse health effects to contain synthetic azo dyes. The presence of dyes impart colour to water,
human body including diabetes, neurological effects, cardiovascular for example methylene blue generate intense blue colour in water, even
diseases, and ultimately cancer of vital organs [1,2]. Arsenic poisoning at dilute concentration. The wastewater discharged into fresh water
is a serious threat to humanity and presence of arsenic in drinking water bodies destructs the aesthetic quality, and also inhibits the penetration
is reported almost all over the world and severely affected regions in- of sunlight which ultimately affects aquatic life [6]. Most of the syn-
clude India, Pakistan, Bangladesh, United states etc. where a significant thetic dyes, being used in textile industries, released into water bodies
fraction of the population, living in these countries, is exposed to ar- are toxic and even carcinogenic to both animals and human beings. In
senic contaminated water having concentration more than WHO addition to the presence of synthetic dyes, the wastewaters released

⁎
Corresponding author.
E-mail addresses: [email protected] (S.I. Siddiqui), [email protected] (S.A. Chaudhry).

https://doi.org/10.1016/j.colcom.2020.100281
Received 31 December 2019; Received in revised form 20 May 2020; Accepted 26 May 2020
2215-0382/ © 2020 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/).
N. Tara, et al. Colloid and Interface Science Communications 37 (2020) 100281

from industries also contain bacteria which create health problems and prepare nanocomposites [31–33].
pose a great threat to human health. These microbes multiply rapidly in However, none of these materials could maintain the quality of
water and for survival consume oxygen which creates oxidative stress water to make it suitable for human consumption. In fact, the materials
on water dependent organisms. Therefore, providing neat and hygienic used in cleaning of water should be multifunctional that have high
water, which is free from arsenic, dyes, bacteria, and have sufficient adsorption capacity to remove pollutants, show antibacterial, and an-
level of oxygen, is the most thoughtful environmental theme of today's tioxidant activities so that bacterial growth can be controlled and de-
world [7]. ficiency of oxygen can be prevented along with cost-effectiveness, and
Thus, the industrial wastewaters need to be treated before dis- nontoxic nature. Moreover, if material is magnetic, which can be easily
charging into water bodies like river, ponds etc. for which numbers of isolated from water post adsorption, then technology generated with
treatment technologies are employed which include ion exchange, ad- application of such material would be best suitable for cleaning of
sorption, electro dialysis, and membrane separation etc. [8]. However, water. In the present case, to achieve such material the magnetic iron
most of these technologies, except adsorption, hardly eliminate above oxide nanoparticles were incorporated into nontoxic, antibacterial and
mentioned water pollutants to make suitable for drinking purpose at all antioxidant black cumin seeds-based organic framework which was
conditions. The adsorption is most economical, efficient, need simple functionalized with graphene oxide. The Nigella sativa seeds (black
affordable paraphernalia and thus easy to apply at domestic level also, cumin) are famous for medicinal properties and have been investigated
and discharge minimum harmful substances, therefore, is most re- thoroughly and reported in the literature [34–36]. Apart from this,
commended technology for eliminating toxic pollutants from water [9]. there are many reports on application of Nigella sativa seeds for effective
A vast variety of solids, which do not dissolve in water, have been removal of charged pollutants from water because of having many
utilized in the past for adsorptive removal of pollutant ions or molecule functional groups at their surface [37–39]. Moreover, preparation of
from water [10–12]. The phenomenon of adsorption, the interaction several nanocomposites by incorporating metal oxide nanoparticles
between a solid surface and a pollutant ion/molecule present in aqu- into these seeds have been reported which have shown good adsorption
eous phase, depends on the numbers of interacting sites at the surface properties [40,41]. But hardly any evidence is available in literature
or extent of surface area of solids. Thus the solid surface having high where both black cumin seeds and graphene/graphene oxide have been
density of functional groups and large area should have high adsorption combined with metal oxide nanoparticles for the development of na-
capability. The nanoparticles having multiple functional groups at their nocomposites for water treatment. Therefore, on the basis of such un-
surface are supposed to be excellent adsorbing materials and their derstanding the nanocomposite formed by using black cumin seeds-
tremendous potential have been utilized in water treatment [13,14]. graphene oxide and iron oxide were expected to be hygienic and sui-
Various types of metal oxides, carbonaceous materials, including table for adsorptive removal of pollutants from water [34]. The pre-
activated carbon, carbon nanotubes, and graphene oxides, have been pared nanocomposite was tested for inhibition of growth of bacterial
functionalized with some organic groups and used and has shown strains, tested for anti-oxidant activities, and employed for adsorptive
higher adsorption capacity [15]. The abundant and inexpensive cellu- removal of representative anionic species, arsenite, and cationic re-
losic plant-based materials can provide carbon framework that may be presentative species, methylene blue dye, from water. The investiga-
modified easily because of having large numbers of functional groups tions established that the prepared nanocomposite has antibacterial,
[16–18]. These carbon frameworks can themselves attract anionic or antioxidant, high adsorption capabilities, magnetic property and are
cationic pollutants from water including dyes and arsenic and thus may abbreviated as BC-GO@Fe3O4 throughout the manuscript.
increase the adsorption capacity of solid materials. Graphene is another
material that can act as carbon frame work and is considered as future 2. Experimental sections
revolutionary material for various admirable applications including
water treatment because of hydrophilicity and mechanical stability 2.1. Materials and methods
[19]. Various metal oxides and graphene have been combined together
to prepare inorganic-organic hybrid nanocomposites with large surface Black Cumin (BC) seeds were purchased from local market of New
area, porous structure, having large number of oxygenated functional Delhi, India. Methylene blue (MB, Mw = 319.85, and λmax 660 nm),
groups that make it extensively useful for photocatalytic degradation graphite flakes, iron salts (FeCl3·6H2O and FeCl2·4H2O), and KMnO4
and adsorption [9,20]. The nanocomposite formed by combining car- were purchased from Sigma-Aldrich, Germany. NaOH and HCl were
bonaceous materials with metal oxide nanoparticles have shown procured from Merck, Germany. All the chemicals were of analytical
amazing results in water treatment due to enhanced porosity, excellent reagent grades and were used as obtained without further purification.
thermal and mechanical properties [5]. Moreover, the combination of All glass wares were washed and cleaned by soaking in dilute HNO3,
metal oxide nanoparticles with carbon framework to produce hybrid and rinsed with double distilled water before use. All solutions were
nanocomposite can also merge magnetic properties in the materials and prepared with deionized water prepared in the laboratory.
the technique represents scientific advancement in water treatment
technology. Few workers have combined metal oxides with graphene 2.2. Preparation
oxides and cellulosic plant-based materials for water removal of pol-
lutants from water [21–23]. Various nanocomposites resulting from 2.2.1. Preparation of graphene oxide
combination of graphene oxide and metal oxides nanoparticles include Graphene oxide was prepared from graphite powder by following
Zr-GO, rGO-zero valent iron, FeOx-GO, monolithic Fe2O3-GO, Hummers method [42]. Briefly, 2.0 g graphite powder was added to
MnFe2O4-GO, CuFe2O4/GO, Fe3O4-rGO-MnO2, GO@iron-aluminium 50 mL of 98% H2SO4 and the mixture was bathed in ice for 30 min to
oxide, nano tin-ferrous oxide decorated GO sheets, CeO2/Fe2O3/gra- maintain temperature below 10 °C, and then 6.0 g powdered KMnO4
phene, hydrous cerium oxide-graphene; and combination of graphene was added slowly under continuous stirring. After 30 min the dark
oxide, metal oxides nanoparticles, and organic constituent includes green suspension was obtained and temperature of reaction mixture
graphene‑carbon nanotube‑iron oxide, β-FeOOH@GO-COOH, poly- was raised to 35–40 °C and continued stirring for 12 h during which
styrene@(+rGO)@GO@Fe3O4, magnetic NPs decorated with cyclo- grey vapours were observed coming out and the mixture became pasty.
dextrin-CDs-functionalized GO, ZnFe2O4/g-C3N4 and Fe3O4/GO/Cu- The resulting mixture was diluted with slow addition of 100 mL of de-
zeolite have been synthesized for the water treatment to remove ha- ionized water and the temperature of the reaction mixture was raised to
zardous pollutants [20,24–30]. The composites mentioned above have 90 °C and continuously stirred for 3 h. The reaction was then termi-
shown higher adsorption capacities than virgin GO or metal oxide na- nated by adding 400 mL of ice cold water containing 10 mL of 30%
noparticles, or plant-based cellulosic materials which have been used to H2O2 solution, then cooled to room temperature. The bright yellow

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N. Tara, et al. Colloid and Interface Science Communications 37 (2020) 100281

Scheme 1. Scheme and inset of preparation of BC-GO@Fe3O4 composite

suspension was washed with 1000 mL of 10% HCl solution, de-ionized established by tuning temperature, time, pH of reaction mixture, dose
water and finally centrifuged for 15 min at 10,000 rpm. The obtained of BC-GO@Fe3O4, and concentrations of As(III) and MB solutions. The
solid residue was washed with distilled water and dried at room tem- adsorption capacity of and percentage sorption of As(III), and MB were
perature for 12 h. calculated by fitting data to the following relationships [42]:

V
2.2.2. Preparation of BC-GO@Fe3O4 The uptake of capacity, Qe = (Co Ce )
m (1)
Washed, cleaned, and grounded black cumin seeds (BC) grains of
size 60/200 mesh, was used as precursor of the composite BC-GO@
Fe3O4which provided the cellulosic template to accommodate the gra- Co Ce
Percentage adsorption = 100
phene oxide and iron oxide (Scheme 1). The preparation of the BC- Co (2)
GO@Fe3O4 was carried out by a simple co-precipitation method.
Briefly, 0.70 g of the prepared graphene oxide, GO, was dispersed in where Co and Ce are concentration, in mg L−1, before and after ad-
300 mL of de-ionized water, and 0.50 g of BC seed powder was added to sorption, respectively. V is the volume of As(III) and MB solution in
300 mL of de-ionized water in a separate beaker. Both suspensions were litre, and m, in g L−1, is amount of BC-GO@Fe3O4 added in solutions as
ultrasonicated for 5 min for complete dispersion and then mixed to- adsorbent. The obtained experimental data was collectively fitted to
gether under constant stirring. In another beaker salts of iron corre- thermodynamic, kinetics, and isotherms relationships, and the para-
sponding to 0.1 M Fe3+ and 0.05 M Fe2+ were added to 100 mL of de- meters obtained from them were used to propose the feasibility, capa-
ionized water and stirred continuously, and the resulting solution was city of BC-GO@Fe3O4, and mechanism of As(III) and MB adsorption.
added drop wise to the above prepared GO and BC suspension. The
stirring was continued for 30 min at 60 °C to insure that the salts of iron
was completely incorporated into the framework of cellulosic and 2.4. Antibacterial studies
carbonaceous templates through chemical interactions. Then 8 M NaOH
solutions were added slowly to the reaction mixture to maintain pH The antibacterial activity of the synthesized BC-GO@Fe3O4 was
around 10.5, and the stirring was continued for other 15 min under investigated against both Gram positive and Gram negative strains. The
similar condition. The black precipitate was obtained in the beaker screening was performed against three different micro-organisms,
which was then cooled to room temperature and magnetically sepa- namely, Gram-negative bacteria (G−), Escherichia coli (E. coli), and
rated, washed several times with excess of distilled water, and dried at Klebsiella pneumonia (K. pneumonia), and Gram-positive bacteria (G+),
room temperature for 48 h [39]. The prepared composite was abbre- Staphylococcus aureus (S. aureus). Agar nutrient was used as medium
viated as BC-GO@Fe3O4 which was subjected to various types of and screening experiments were performed by following paper disk
characterizations to analyse the physiochemical properties and then diffusion method [39]. The calculated volumes of BC-GO@Fe3O4 so-
was investigated for the antibacterial and antioxidant activities and lution were loaded on the paper discs then these discs were fixed on a
then employed for adsorption studies. lawn of bacteria in a Petri-dish. The growth medium was already
sterilized by autoclaving at 120 °C for 30 min. The paper discs im-
2.3. Adsorption studies pregnated with BC-GO@Fe3O4 was placed on the solidified medium in
the Petri-dish and were pre-incubated for 1 h at room temperature and
For investigating the adsorption capability of the prepared BC-GO@ further incubated at 37 °C for 48 h for anti-bacterial action. The sus-
Fe3O4 batch mode experiments were carried out under various condi- ceptibility of the bacteria against BC-GO@Fe3O4 was estimated by
tions using 10 mL of aqueous solutions of As(III) and MB, separately. measuring the distance of zones of inhibition around the discs.
The optimum conditions for the adsorption experiments were

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N. Tara, et al. Colloid and Interface Science Communications 37 (2020) 100281

2.5. Evaluation of in vitro antioxidant activity test compound. The total reducing capability of BC-GO@Fe3O4 was
estimated by following Oyaizu protocol with minor modification [46].
Several in vitro methods, available for evaluating the antioxidant The cocktail of the reaction was prepared by taking 2.5 mL phosphate
activity, were applied to check antioxidant capability of BC-GO@Fe3O4 buffer of pH 6.6, and 2.5 mL of K3Fe(CN)6 (1% w/v) which were added
and for that L-ascorbic acid (L-AA) was selected as reference anti- to solution of different concentrations of BC-GO@Fe3O4 in the range
oxidant. In vitro antioxidant test involved scavenging of free radical, 25–800 μg mL−1. The reaction mixture was mixed thoroughly and kept
DPPH (1,1-diphenyl-2-picrylhydrazyl), nitric oxide, and total reduction in water bath for 20 min at 50 °C. 2.5 mL of (10% w/v) trichloro acetic
capability as discussed herein. acid was added to each tube after incubation. Further, the tubes were
DPPH, a stable free radical, because of delocalisation of odd electron centrifuged at 3000 rpm for 10 min to settle down the solid sediments
over the whole molecule, gives rise to deep violet colouration in ethanol and supernatants were collected for next step. The collected super-
solution and absorbs at 517 nm. If a substrate, capable of donating natant was added to 0.5 mL of FeCl3 (0.1%, w/v) and 2.5 mL of distilled
hydrogen ion, is added to DPPH solution it reduces DPPH resulting into water. The formation of chromophores was observed and the activity of
loss of violet colour and absorbance of solution decreases. The change reaction was measured by taking absorbance at 700 nm. Increase in the
in absorbance before and after the reaction with a compound gives optical density of the solution expresses the reducing power of BC-GO@
DPPH scavenging activity. The free radical scavenging activity of the Fe3O4.
BC-GO@Fe3O4 was compared with L-ascorbate by following Blois
method [43]. 40 μL of working stock solution containing 25–800 μg of
BC-GO@Fe3O4 and L-ascorbate were taken in different test tubes. The 3. Results and discussion
reaction mixture was prepared in methanol and the volume was ad-
justed to 3 mL. Thereafter 150 μL of DPPH solution (0.1 mM) was added 3.1. Characterization
to each tube and mixed by vortexing in dark and the reaction mixture
was incubated for 20 min at room temperature. For the correction of The previously published literature revealed that the FT-IR spec-
baseline the optical density of the control sample was measured which trums of BC seeds indicate plenty of absorption peaks for BC framework
was prepared by mixing 40 μL of DMSO and 1.96 mL of methanol. The which have been attributed to the presence of hydroxyl (-OH), carboxyl
scavenging activity, measured by taking absorbance at 517 nm, ex- (-COOH), Carbonyl (C=O), and amides I and II (C]O and -NH) func-
pressed in percentage, was calculated by fitting absorbance data in the tional groups [37–42]. Further, the FT-IR spectrums of graphene oxide
following formula: sheets show the characteristic peaks for -OH, C]O, -C-O, -C=C-
stretching, and -C-H deformation vibrational bands [9,24]. The pre-
% Inhibition of DPPH radical sence of almost all the peaks corrosponding to various groups were
absorbancecontrol absorbancesample retained in spectrum of nanocomposite BC-GO@Fe3O4, however, some
= x100 shifting have also been observed due to interactions of these functional
absorbancecontrol (3)
groups on BC, GO with Fe3O4 nanoparticle. Moreover, some new peaks
The concentration of BC-GO@Fe3O4 which scavenges 50% radicals appeared for Fe3O4 nanoparticles in the spectrum of naocomposite
is referred to as IC50 value. [9,24,42].
The antioxidant activity of BC-GO@Fe3O4 was also investigated by The FT-IR spectrum of BC-GO@Fe3O4 (Fig. 1) showed character-
following Griess Ilosvoy reaction with minor modification in which istics vibration bands at 3435, 2929, 2843, 1634, 1549, 1401, 1069,
nitric oxide (NO) scavenging activity was determined in solution [44]. 570, and 451 cm−1. The broad peak around 3435 cm−1 appeared due
The intensity of the colour is proportional to the quantity of nitrite to -O-H stretching vibrational frequency of hydroxyl group on BC, GO
formed. Sodium nitroprusside, SNP, decomposes in aqueous solution to organic frameworks and Fe3O4 nanoparticles. The broadening might be
generate NO radicals at physiological pH (7.2) which under aerobic due to interaction, through H-bonds, of hydroxyl groups on various
conditions reacts with oxygen to produce nitrite ion. This nitrite ion components of the nanocomposite. The two sharp peaks at 2929 and
reacts with Sulfanilic acid under acidic conditions to form diazonium 2843 cm−1 gave the evidence for -C-H stretching vibrations of CH3 and
salt, which couples with N-(1-Naphthyl) ethylene-di-amine to form red CH2 groups present on some compounds, like Thymohydroquinone,
coloured azo dye whose concentration can be measured from the ab- Thymol and Limonene, in black cumin seed [35]. The peaks around
sorbance at 550 nm. For the experiment the reaction mixture was 1634 and 1549 cm−1 appeared for the -C=O and NeH bond stretching
prepared in glass test tubes by taking 1.0 mL of 10 Mm phosphate buffer
saline, PBS, of pH 7.4, 10 mM SNP, and 25–800 μg BC-GO@Fe3O4
dissolved in DMSO. The same procedure was followed for the pre-
paration of standard antioxidant for positive control. All the reaction
mixtures were mixed thoroughly by vortexing the tubes gently. The
tubes were incubated for 2 h at 30 °C and then 0.5 mL of Griess reagent
was added to each tube. The appearance of pink colour formation was
evaluated by taking absorbance of the reaction mixture at 550 nm. The
reduction in the formation of nitric oxide by antioxidant BC-GO@Fe3O4
was calculated using formula given below:

Ao At
%Inhibition of NO radical = x100
Ao (4)

where Ao and At are the absorbance of mixture before reaction and after
reaction at different concentrations of BC-GO@Fe3O4 with Griess re-
agent [45].
The antioxidant activity of BC-GO@Fe3O4 was also investigated by
following another method in which an antioxidant forms a coloured
complex with potassium ferricyanide, trichloro acetic acid, and ferric
chloride, that absorbs at 700 nm. The increase in absorbance of the
reaction mixtures indicates an increase in the antioxidant activity of the Fig. 1. FT-IR spectrum of BC-GO@Fe3O4.

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N. Tara, et al. Colloid and Interface Science Communications 37 (2020) 100281

Fig. 2. XRD pattern of GO, BC, Fe3O4 and BC-GO@Fe3O4.

vibrational frequencies of amide groups present on black cumin seeds, D=

K
respectively. The band at 1401 cm−1 might be assigned to the sym- Cos (5)
metrical stretching of -C-O- group present may be in amide II functional
group or ethereal part. The bands in range 1069 cm−1 appeared for -C- where K = 0.9 is the shape factor, λ is X-ray wavelength of Cu K ra-
O stretching frequency. In addition to the characteristic peaks of diation (0.154 nm), θ is the Bragg diffraction angle, and β is full width
functional groups, the BC-GO@Fe3O4 also showed two stretching vi- at half maxima (FWHM) of respective diffraction peak.
bration bands at 570 and 451 cm−1 which might be due to the presence The SEM images of BC-GO@Fe3O4 (Fig. 3a) showed the hetero-
of iron‑oxygen (FeeO) vibrational frequency and confirmed that the geneous, irregular, and porous surface having agglomerated Fe3O4
synthesized nanoparticles were iron oxide. Moreover, the shifting in the nanoparticles grown in the organic framework of GO and BC. The EDX
characteristics peaks and disappearance of -C=O stretching frequency, spectrum associated to the SEM image (Fig. 3b) gave the elemental
assigned for the organic framework, was also found in the FT-IR spec- composition of the prepared BC-GO@Fe3O4 comprising C (22.52 wt%),
trum of BC-GO@Fe3O4 which indicated strong interaction of oxygenous O (53.44 wt%), and Fe (20.27 wt%). However, the EDX spectrum didn't
organic framework and Fe3O4 nanoparticles through electrostatic and show peak corresponding to nitrogen although it's presence has been
hydrogen bonding [42]. These shifting of peaks further confirmed the confirmed as amide group in IR spectrum. In fact the the extent of
preparation and the presence of large numbers of functional sites on the presence of element N is to very low in weight % and it's peak might
surface of the prepared BC-GO@Fe3O4. had overlapped with high weight % peak of C which might have faded
The X-ray diffraction pattern of GO (Fig. 2, GO) showed char- the peak of N thereby no N peak could be detected [49].
acteristic peak for carbon (001) sheets at 15°(2θ) with d-spacing or The TEM images (Fig. 4) showed the morphology of Fe3O4 having
inters layer distance of 8.33 Ǻ. The X-ray diffraction of BC (Fig. 2, BC) cubic structure with particle size in the range 30–42 nm. The TEM
revealed the cellulosic structure of seeds having characteristic broad image also showed that the Fe3O4 nanoparticles are embedded in the
peaks around 18–22° (2θ) corresponding to the (002) plane. The X-ray carbon framework of GO and BC.
diffraction pattern of Fe3O4 nanoparticles (Fig. 2, Fe3O4) and BC-GO@ The thermogravimetry analysis, TGA, graph (Fig. 5) showed the
Fe3O4 nanocomposite (Fig. 2, BC-GO@Fe3O4) showed the character- curve having two weight losses on heating in the temperature range of
istics peaks of Fe3O4 in angular range 10–80° (2θ) which corresponded 0–700 °C under nitrogen atmosphere. The first phase of the curve in-
to the plane (220), (311), (400), (422), (511), and (440) and were in- dicated weight loss, in the temperature range 100–200 °C, might be due
dexed with JCPDS card No.19–0629, and confirmed the growth of cubic to evaporation of volatile compounds like moisture and oils; and the
structure of Fe3O4 crystals in the GO and BC frameworks [47]. The less second phase of the curve continued till 700 °C which showed de-
intense peaks in XRD pattern suggested the poor crystalline nature of gradation of organic template framework on pyrolysis. Under N2 en-
BC-GO@Fe3O4 particles whose average crystallite size, determined vironment, the solid residues can also be formed but this was ignored,
from the Scherer equation given below, was found to be 95.10 nm then the total loss in weight of BC-GO@Fe3O4 on pyrolysis was about
[42,48]. 33% (6.3 to 4.3 g). The TGA curve indicated the high thermal stability
of the prepared BC-GO@Fe3O4 in the temperature range of 100–200 °C.
The specific saturation magnetization, Ms., of the prepared BC-GO@

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N. Tara, et al. Colloid and Interface Science Communications 37 (2020) 100281

Fig. 3. a SEM images of BC-GO@Fe3O4 at 1500, 3000, 10,000 and 30,000 magnifications. b EDX plot of BC-GO@Fe3O4 nanocomposite.

Fe3O4 was calculated at room temperature through Vibrating-Sample The zero point charge, pHzpc, of BC-GO@Fe3O4 was determined by
Magnetometer (VSM) measurement (Fig. 6), which was found to be following previously reported salt addition method, and was found to
approximately 10.0 emu g−1 with small remanence and coercivity [50]. be 7.25. The pHzpc value near to neutral pH indicates the advantage of
The VSM analysis established a near superparamagnetic behaviour of BC-GO@Fe3O4 for both cationic and anionic pollutants removal from
BC-GO@Fe3O4. Although, the value of Ms. is found to be much lower water.
than that reported in previously published studies for bulk magnetite
which might be due to the small size of magnetite nanoparticles and the 3.2. Batch adsorption studies
presence of non-magnetic GO and BC in the composite [51,52]. How-
ever, the magnetic behaviour and biological activity of BC-GO@Fe3O4 The batch based experiments were performed to determine the
suggested its advantageous application for water treatment because of adsorption capacity of BC-GO@Fe3O4 for As(III) and MB under the in-
post adsorption magnetic separation capability over the filtration and fluence of various reaction parameters. The known fact is that the in-
centrifugation, controlled growth of bacteria and maintaining oxygen in crement in the amount of adsorbent increases the rate of adsorption due
treated water. to enhancement in the adsorption sites which affect the removal

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N. Tara, et al. Colloid and Interface Science Communications 37 (2020) 100281

Fig. 4. TEM images of BC-GO@Fe3O4.

solution having 1.0 mg L−1 concentration. Whereas, the adsorption

increased from 93 to 97% on increasing the dosage from 0.5 to
1.0 g L−1 from MB solution having 10 mg L−1 concentration. The
equilibration in adsorption of both As(III) and MB, from their respective
solutions, might be the results of saturation of adsorption sites and no
further adsorption was possible, therefore, 1.0 g L−1 dose of BC-GO@
Fe3O4 was optimum for As(III) and MB solutions of 1.0 and 10 mg L−1
concentration, respectively [50].
The enhancement in the concentration of As(III) from 0.1 to
1.0 mg L−1; and that of MB from 10 to 45 mg L−1 indicated merely
slight change in the adsorption capacity of BC-GO@Fe3O4 for both As
(III) as well as MB. For MB, the adsorption decreased from 99 to 96% on
increasing concentration from 10 to 45 mg L−1; and for As(III) it was in
the similar range at concentration level 0.1 to 1.0 mg L−1. These results
might be due to the large numbers of adsorptive sites on the BC-GO@
Fe3O4 surface, which provided the large attractive sites for adsorption
of both MB and As(III). Therefore, dosage and concentration optimi-
zation results suggested that only small amount of BC-GO@Fe3O4 was
sufficient for MB and As(III) removal from low or higher concentra-
Fig. 5. TGA graph of BC-GO@Fe3O4.
tions. However, the concentration of As(III) has been kept in the range
0.1–1.0 mg L−1 because most of the previous studies [30,53] have
9.5 suggested the better results for removal at high concentrations rather
than low concentration due to the low selectivity of adsorbents.
Therefore, this study was carried out with low concentration of As(III),
and BC-GO@Fe3O4 showed high selectivity and efficiency towards As
Magnezaon (emu g-1)

4.5
(III) at low concentration.
The pH of water showed a significant influence on the adsorption
capacity of BC-GO@Fe3O4 for As(III) and MB which was because of
-0.5
-2.2 -1.2 -0.2 0.8 1.8 charge orientations on these species during the process [39]. It is well
known fact that pH of water may alter the charge orientation of an
adsorbent as well as adsorbate, thus influence the rate of adsorption.
-5.5
The effect of pH on the removal of As(III) and MB from their aqueous
solutions was investigated in the pH range 2–10. The decline in the
percentage removal of MB with decrease in the pH of the solution was
-10.5
observed. The fact behind this behaviour might be enhancement in the
Magnec Field (T) electrostatic repulsion between positively charged surface of BC-GO@
Fe3O4 (BC-GO@Fe3O4-OH2+) formed due to protonation and cationic
Fig. 6. VSM plot of BC-GO@Fe3O4 nanocomposite.
nature of MB ions at acidic pH. As the pH of solution was increased the
functional sites on the BC-GO@Fe3O4 surface were deprotonated which
capacity for the pollutants from water. For this study, the similar ob- led to the enhancement in the electrostatic attraction between overall
servation was observed which suggested that on enhancing amount of negatively charged surface (BC-GO@Fe3O4-O−) and positively charged
BC-GO@Fe3O4 the removal efficiency increased for both As(III) and MB MB ions, thus alkaline pH of the solution was most suitable for higher
ions. The As(III) adsorption increased from 83 to 96% on enhancing BC- MB adsorption. However, the change of pH of water didn't influence the
GO@Fe3O4 dosage from 0.5 to 1.0 g L−1, and equilibrated, from adsorption efficiency for MB significantly. The observation might

7
N. Tara, et al. Colloid and Interface Science Communications 37 (2020) 100281

suggest the existence of H-bonding between MB and BC-GO@Fe3O4 The RL values were found in the range 0–1 which suggested the
which is supposed to be hardly affected on changing pH. However, As favourability of the process in the test temperature range for both As
(III) is found in the form of H3AsO3, H2AsO3− and HAsO32− in aqueous (III) and MB ions. These values of RL indicated the higher favourability
medium whose adsorption percentage was higher at acidic pH which of As(III) and MB adsorption at 27 °C. However, the regression coeffi-
might be due to attraction of these ions towards protonated BC-GO@ cient, R2, showed the poor fitting of data to Langmuir model for As(III)
Fe3O4 surface (BC-GO@Fe3O4-OH2+). On increasing the pH of solution {R2 in range 0.84–0.87} and for MB{in range 0.98–0.94} showed
the adsorption of As(III) decreased which might be due to electrostatic comparatively better fitting of data at lower temperature. The sorption
repulsion between oxy anion of arsenic and deprotonated BC-GO@ data was then investigated by applying to the Freundlich isotherm, with
Fe3O4-O− surface [24,25]. the expectation that the surface of BC-GO@Fe3O4 might be hetero-
geneous and multiple layer formation of by both MB and As(III) could
3.3. Thermodynamic investigation be possible, which in linear form is given as follows:
1
The effect of temperature on the adsorption of As(III) and MB onto log Qe = log kF + log Ce
n (10)
BC-GO@Fe3O4 surface was investigated from solutions having con-
centration in the range 0.1–1.0 mg L−1 of As(III); and 10–45 mg L−1 of where kF and n, the Freundlich constants, were determined from the
MB, at 27, 35 and 45 °C. The investigation suggested that with upstairs plot logQe versus logCe (Fig. 7b). The kF gives an idea about the sorption
of temperature the adsorption of both As(III) and MB decreased which capacity, and was in the range 3.52–1.43 mg(1-n) Ln g−1 for As(III); and
might be due to the existence of weak bonding between these ions and 31.99–21.20 mg(1-n) Ln g−1 for MB. The n values, found in the range
BC-GO@Fe3O4 surface which break up at higher temperature. 1–10, suggested the favourability of both ions adsorption at 27–45 °C
Thermodynamic parameters, calculated from the mathematical re- temperature range. The R2 values of Freundlich isotherm plots for both
lationships given below, can put the strong evidence for the feasibility, As(III) and MB were found to be higher than Langmuir plots and near to
and spontaneity of MB and As(III) adsorption onto the BC-GO@Fe3O4 unity which suggested that the Freundlich isotherm provided more
surface [5,48]. consistent conformity to the equilibrium adsorption data and confirmed
the heterogeneity of BC-GO@Fe3O4 surface (Table 1).
Go = H o So (6) The attraction and probability of adsorption of As(III) and MB onto
Go = RT ln K C (7) BC-GO@Fe3O4 heterogeneous surface was determined by fitting data in
Temkin isotherm, which is given below:
Gibbs free energy was calculated and found with negative indica-
RT RT
tion, −7.80, −5.70, and − 3.85 kJ mol−1 for As(III); and − 10.85, Qe = ln AT + ln Ce
bT bT (11)
−9.65, and − 8.60 kJ mol−1 for MB adsorption, at 27, 35 and 45 °C,
respectively and separately, which suggest the feasibility and sponta- where coefficients AT and bT indicate binding energy and heat of ad-
neity of adsorption of both ions in the temperature range. The enthalpy sorption, respectively, and were obtained from the slope and intercept
of adsorption was also positive, +73.10 kJ mol−1 for As(III); of Qe versus lnCe plots (Fig. S1). The AT values for MB increased slightly
and + 48.20 kJ mol−1 for MB which suggested the endothermic nature from 0.136 to 0.138 L g−1 when solution temperature was increased
of the adsorption process. The negative indications of entropy change, from 27 to 45 °C, indicating nearly similar binding energy at tested
−0.22 kJ mol−1 K−1 for As(III) and − 0.12 kJ mol−1 K−1 indicated temperature range. The bT values for MB also remained almost similar,
the decrease in the randomness during the adsorption of these ions. The 0.112 to 0.121 kJ mol−1 (Table 1), which suggested nearly same heat of
decrease in entropy at interface suggested electrostatic or physical in- adsorption, i.e., similar bonding probability of MB with BC-GO@Fe3O4
teraction between As(III) and MB with BC-GO@Fe3O4. in the temperature range 27–45 °C. Whereas, for As(III) adsorption the
AT values remained almost constant in the range 1.21 to 1.25 L g−1
3.4. Effect of temperature and isotherm study which indicated almost similar binding energy in the temperature range
27–45 °C. The bT value, however, decreased slightly from 0.628 to
To find out the maximum adsorption capacity, affinity of As(III) and 0.552 kJ mol−1, which suggested slightly lower heat of adsorption, i.e.,
MB towards BC-GO@Fe3O4, and to predict the role of temperature and slightly lower bonding probability of As(III) with BC-GO@Fe3O4 at
concentration the sorption data was investigated by fitting in various higher temperature.
isotherms, which include Langmuir, Freundlich, Temkin, and Dubinin- Another mathematical relationship, given below, referred to as
Radushkevich models. Assuming the surface of BC-GO@Fe3O4 as Dubinin-Radushkevich isotherm, was used to determine the nature of
homogeneous and formation of monolayer around the its surface by bonding between As(III) and MB and BC-GO@Fe3O4.
both As(III) and MB, the equilibrium adsorption data was modelled
ln Qe = ln QD R
2
(12)
with the Langmuir isotherm which is given below:
where β is a constant that was used to determine the free energy change
Ce C 1
= e + (ED-R) involved during the interaction between As(III) and MB and BC-
Qe Qo Qo b (8)
GO@Fe3O4, and the Polanyi potential, ε, was calculated from the fol-
−1 −1
where Ce (mg L ) and Qe (mg g ) are concentration and amount of lowing expressions:
As(III) and MB adsorbed onto the surface of BC-GO@Fe3O4 at equili-
ED =( 2 ) 0.5
(13)
brium, respectively. b is Langmuir constant (L mg−1) that defines the
R

adsorption affinity of MB and As(III) towards surface, and Qo (mg g−1) 1

is Langmuir adsorption capacity for formation of monolayer around BC- = RT ln 1 +
Ce (14)
GO@Fe3O4. The plot of Ce/Qe versus Ce (Fig. 7a) gave values of Qoin the
range 1.41–1.73 mg g−1 for As(III); and 87.71–125.0 mg g−1 for MB in The QD-R for MB was found between 37.525 and 38.664 mg g ; and −1

the temperature range 27–45 °C (Table 1). The b values were also cal- that for As(III) was 0.530 and 0.805 mg g−1, which indicated nearly
culated and used to determine the values of separation factor, RL, by similar MB adsorption capacity in between 27 and 45 °C (Fig. S2); and
employing the following equation [48]: that increased for As(III) adsorption with the increase in temperature in
1 the same range and are listed in Table 1. The ED-R for MB adsorption
RL = ranged between 1.003 and 1.984 kJ mol−1; and that for As(III) ranged
(1 + bCo ) (9)
6.804–4.939 kJ mol−1 in the temperature range 27–45 °C (Table 1).

8
N. Tara, et al. Colloid and Interface Science Communications 37 (2020) 100281

0.25 0.06

0.2
0.05
0.15
0.04
Ce/Qe

Ce/Qe
0.1 As(III)/27 °C MB/27 °C
0.05 35 °C 0.03 35 °C
45 °C
45 °C
0 0.02
0 0.05 0.1 0.15 0.2 0.1 0.6 1.1 1.6 2.1 2.6
Ce Ce
(a)

-2.9 -2.4 -1.9 -1.4 -0.9

-0.2 1.7
As(III)/27°C MB/27 °C
35 °C -0.4 35 °C
1.5
45 °C -0.6 45 °C

logQe
logQe

1.3
-0.8

-1
1.1
-1.2
0.9
-1.4
-0.7 -0.2 0.3
(b) logCe logCe

Fig. 7. a Langmuir adsorption isotherm plots for As(III) and MB adsorption. b Freundlich isotherm plots for As(III) and MB adsorption.

The ED-R range indicated strong interaction of As(III) with BC-GO@ full filled and upcoming ions needed specific way to interact which
Fe3O4 and weak that for MB; and in both ions interactions the energy declined the rate of adsorption. For understanding the of mechanism of
was less than 8.0 kJ mol−1 suggesting physical nature of sorption of MB As(III) and MB adsorption and kinetics of the reaction, the two most
and As(III) ions onto BC-GO@Fe3O4. The conclusion can be made from prevalent kinetics models, pseudo-first order and pseudo-second order,
Isotherm investigation that the surface of BC-GO@Fe3O4 was com- as given below, were applied to time dependant adsorption data [42]:
paratively heterogeneous and As(III) and MB interaction was of phy-
k1
sical nature. log(Qe Qt ) = log Qe t
2.303 (15)

t 1 t
3.5. Adsorption kinetics = +
Qt k2 Qe 2 Qe (16)

Effect of duration of reaction on the adsorption of As(III) and MB where Qe and Qt are the amounts of As(III) and MB adsorbed onto BC-
was investigated by varying contact time in the range 15–150 min after GO@Fe3O4 at equilibrium, and at time t. k1(min−1), and k2
adding 1.0 g L−1 dosage of BC-GO@Fe3O4 to As(III) solution having (g mg−1 min−1) are the pseudo-first, and pseudo-second order rate
1.0 mg L−1 concentration, and 10 mg L−1 that of MB. The time de- constants, respectively. The plots of pseudo-first order and pseudo-
pendent data for both As(III) and MB suggested that the adsorption second order (Fig. S3) gave relative parameters including k1, k2, Qe and
proceeded in two stages. The first stage was fast due to availability of R2 for both As(III) and MB ions and are given in Table 2. Results sug-
significant vacant sites on the surface of BC-GO@Fe3O4 which provided gested that, for both As(III) and MB adsorption, good conformity of
large space for interaction to As(III) and MB ions without any difficulty, linear plots was achieved for pseudo-second order kinetics with higher
followed by the second slow step after 15 min for both As(III) as well as and close to unity value of R2. Further, the calculated theoretical ad-
MB because almost all vacant sites on the BC-GO@Fe3O4 surface were sorption capacities values, Qe(cal.) for As(III) was 1.01 mg g−1; and that

Table 1
Isotherm parameters for As(III) and MB adsorption onto BC-GO@Fe3O4.
Pollutant Temp. (°C) Langmuir Freundlich Temkin Dubinin-Radushkevich

Qo (mg g−1) b (L mg−1) RL R2 kF mg(1- n R2 AT (L g−1) BT (kJ mol−1) R2 QD-R β (mol2 kJ−2) E (kJ mol−1) R2
n) n
L (mg g−1)
g−1

MB 27 87.71 0.610 0.102 0.98 31.99 1.37 0.99 0.136 0.112 0.96 37.53 −0.492 1.008 0.92
35 119.04 0.285 0.259 0.88 25.81 1.23 0.99 0.137 0.117 0.96 42.15 −0.127 1.984 0.95
45 125.0 0.210 0.322 0.94 21.20 1.23 0.99 0.138 0.121 0.96 38.66 −0.147 1.844 0.90
As(III) 27 1.417 36.739 0.002 0.84 3.52 1.52 0.99 1.21 0.628 0.88 0.805 −0.011 6.804 0.98
35 1.433 10.571 0.009 0.94 1.85 1.41 0.99 1.21 0.628 0.93 0.613 −0.016 5.625 0.99
45 1.733 4.149 0.023 0.87 1.43 1.28 0.99 1.25 0.552 0.91 0.53 −0.021 4.939 0.98

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N. Tara, et al. Colloid and Interface Science Communications 37 (2020) 100281

Table 2
Kinetic parameters for the adsorption of MB and As(III) onto BC-GO@Fe3O4.
Pollutant Pseudo-first order Pseudo-second order Film diffusion model Intraparticle diffusion model

−1 2 −1 −1 2 −1 −1 2
k1 min Qe (cal) R k2 g mg min Qe (cal) R kfd mg g min Intercept R kipd mg g−1 min-0.5 Intercept R2
mg g−1 mg g−1

MB (Qe (exp.) = 9.87 mg g−1) 0.021 3.315 0.90 0.0002 10.03 1.0 0.023 1.024 0.90 0.239 8.090 0.97
As(III) (Qe 0.210 197.97 0.54 6.758 1.010 1.0 0.125 0.028 0.83 0.0287 0.647 0.86
(exp.) = 0.950 mg g−1)

for MB was 10.03 mg g−1; which was more consistent to the experi-
mental values of Qe (exp.), for As(III) it was 0.958 mg g−1; and that for 100
MB was 9.87 mg g−1. Thus, it could be concluded that the adsorption
MB
80
behaviour of MB and As(III) could be well described by using pseudo-

Adsorption %
As(III)
second order kinetic relationship. The results indicated the specific 60
chemical interaction between MB and As(III), and BC-GO@Fe3O4. 40

3.6. Mechanistic modelling 20

0
The prediction of the step which determining the rate of an ad- 1 2 3 4 5
sorption system is considered as an important tool for proper designing Number of adsorption-desorption cycle
of a water treatment system. The sorption process may involve any one
Fig. 8. Reutilization study of regenerated BC-GO@Fe3O4.
of three main rate limiting steps, viz., crossing of liquid film, formed
around the solid surface, by adsorbate ions from aqueous phase, that
may control the whole process; the diffusion of adsorbate into the pores parameters which used for comparison with other reported adsorptive
on the surface of adsorbent; and the adsorption of the adsorbate on the materials. It can be deduced from the Table 3, that highly functiona-
capillary spaces and interior surfaces of the adsorbent pores [39]. The lized, magnetically separable, and recyclable BC-GO@Fe3O4 showed
first two steps are slow while third step is very rapid which may not higher adsorption capacity at equilibrium for MB as well as As(III) in
control the process. The adsorption of As(III) and MB onto BC-GO@ comparison to the reported adsorbents (Table 3). The higher adsorption
Fe3O4 was rapid, therefore, can be controlled by the liquid film for- capacity of BC-GO@Fe3O4 at equilibrium might be due to presence of
mation and/or diffusion of adsorbate into the pores on the solid surface. highly dense functional sites on graphene oxide-black cumin seeds and
Thus, for determination of rate controlling step, the intraparticle dif- smaller size of Fe3O4 nanoparticles in the nanocomposite [54,55].
fusion, and film diffusion models as given below, respectively were
used to fit data [48]: 3.9. Antibacterial activity
Qt = kipd t 0.5 +C (17)
The 2.0 mg mL−1 stock solution of BC-GO@Fe3O4 was prepared in
ln(1 F) = kfd t (18) 10% methanol and out of this stock solution the various volumes (Table
S1) were loaded on the paper discs which caused the significant in-
−1 -0.5 −1 −1
where kipd (mg g min ) and kfd (mg g min ) are the rate con- hibition of growth of tested bacterium cells (Fig. S4). The inhibition
stants of intraparticle diffusion and film diffusion processes, respec- zone values indicated that BC-GO@Fe3O4 controlled the growth of
tively. The constant C is related to the thickness of the film around the E.coli, K. pneumonia, and S. aurous significantly but controlled S. aurous
solid particles and F = Qt/Qe represents the fractional attainment of slightly more effectively. From the investigations it can be concluded
equilibrium. Various parameters, obtained from the above relation- that BC-GO@Fe3O4 is capable to control the growth of bacteria and thus
ships, are depicted in Table 2 which suggested that both intraparticle as is highly suitable for water treatment containing bacteria also.
well as film diffusion processes partly controlled As(III) and MB ad-
sorption onto the BC-GO@Fe3O4 [39,40,48]. 3.10. Antioxidant application

3.7. Regeneration and reuse of BC-GO@Fe3O4 The observations obtained from antioxidant activity investigation,
by employing DPPH, Nitric oxide, and Total reduction capability assays,
The regeneration and cyclic usability of BC-GO@Fe3O4 for As(III) have shown encouraging results (Fig.S5 (a-c). The DPPH free radical
and MB sorption was also investigated for five consecutive adsorption- scavenging activity of BC-GO@Fe3O4 was performed in the concentra-
desorption cycles. The desorption experiments were performed with tion range 25–800 μg mL−1 (Fig. S5a) and was found to increase with
1 M NaOH solution for MB desorption; and that with 1 M HCl solution the dosage of BC-GO@Fe3O4. The free radical activity results were
for As(III) by taking 2.0 g L−1 of BC-GO@Fe3O4 in optimized con- compared with standard antioxidant, L-Ascorbate (L-AA). The DPPH
centration of MB and As(III) [50]. After the fifth adsorption-desorption free radical inhibition by BC-GO@Fe3O4 was found to be
cycle the adsorption capacity of BC-GO@Fe3O4 decreased to 45% for 82.23 ± 0.014 at 800 μg mL−1 concentration and was slightly lower
MB and 25% for As(III) (Fig. 8). Therefore, BC-GO@Fe3O4 showed the than that of L-AA (98.04 ± 0.01) under similar conditions. The IC50
good adsorption capacity even after fifth adsorption-desorption cycle. value of BC-GO@Fe3O4 was found to be 58.47 ± 2.36 μg mL−1
(P < .0001) and that of L-AA was 45.02 ± 1.98 μg mL−1 which
3.8. Comparative studies suggested that BC-GO@Fe3O4 possesses significant free radical
scavenging activity.
Although the adsorption of As(III) and MB followed Freundlich At the same time the Nitric oxide radical scavenging activity of BC-
isotherm but for comparison purpose the Langmuir isotherm capacities GO@Fe3O4 and standard antioxidant, L-AA, were performed at the si-
of BC-GO@Fe3O4 were used. The kinetics, initial concentrations, reac- milar concentration range (Fig. S5b). The Nitric oxide radical scaven-
tion time, optimized dosage, pH and temperature were the other ging effect of BC-GO@Fe3O4 and L-AA increased with the dosage of BC-

10
N. Tara, et al. Colloid and Interface Science Communications 37 (2020) 100281

Table 3
Comparative evaluation of various adsorbents applied for As(III) and MB removal.
Adsorbate Adsorbent Initial concentrations Reaction time Optimized adsorption dose, m Temp. (°C) pH Qe (mg g−1) Ref.
(mg L−1) (min) (g L−1)

MB Black cumin (Acid 10.0 120 1.0 27 7.0 9.97 [37]

washed)
Fe2O3-ZrO2/BC 10.0 120 3.0 27 7.0 0.45 [39]
MnO2/BC 10.0 120 1.0 27 7.0 9.97 [40]
Fe2O3-SnO2/BC 10.0 120 2.0 27 7.0 4.92 [41]
MnFe2O4/BC 10.0 120 3.0 27 7.0 3.32 [42]
BC-GO@Fe3O4 10.0 150 1.0 27 7.0 10.0 This Study
As(III) Fe2O3-ZrO2/BC 1.0 120 2.0 27 7.0 0.45 [39]
ZrO2 coated sand 0.8 90 7.0 27 7.0 0.11 [54]
Fe2O3-SnO2 coated sand 1.0 120 8.0 27 7.0 0.06 [55]
BC-GO@Fe3O4 1.0 150 1.0 27 7.0 1.0 This Study

GO@Fe3O4 and L-AA. The maximum percentage of nitric oxide radical Appendix A. Supplementary data
scavenging effect obtained were 83.28 ± 0.22 and 73.39 ± 2.014 by
L-AA and BC-GO@Fe3O4, respectively, at 800 μg mL−1. The IC50 values Supplementary data to this article can be found online at https://
for BC-GO@Fe3O4 and L-AA were 48.9 ± 2.3 μg mL−1 and doi.org/10.1016/j.colcom.2020.100281.
58.26 ± 2.48 μg mL−1 (p < .0001) which again showed that BC-
GO@Fe3O4 possessed nitric oxide radical scavenging activity also. References
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