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Environmental Research 178 (2019) 108667

Contents lists available at ScienceDirect

Environmental Research
journal homepage: www.elsevier.com/locate/envres

Nigella sativa seed based nanohybrid composite-Fe2O3–SnO2/BC: A novel T


material for enhanced adsorptive removal of methylene blue from water

Sharf Ilahi Siddiqui, Fatima Zohra, Saif Ali Chaudhry
Environmental Chemistry Research Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi, India

A R T I C LE I N FO A B S T R A C T

Keywords: In this work, an advance approach is reported for the water treatment technology using nanohybrid composite
Water treatment Fe2O3–SnO2/BC prepared by incorporation of iron-tin binary oxide into the cellulosic framework of medicinally
Adsorption active Nigella sativa (Black cumin) seed powder. The co-precipitation method was followed to prepare the na-
Composite nohybrid composite which was subjected to investigate its physiochemical properties using spectroscopic and
Fe2O3–SnO2/BC
microscopic techniques. Fourier-transform infrared spectroscopy analysis confirmed the formation of highly
Methylene blue
functionalized nanocomposite through the hydrogen and electrostatic interactions between the functional
groups of seeds and Fe2O3–SnO2. X-ray and selected area electron diffraction pattern revealed the presence of
cubic phase of γ-Fe2O3 and tetragonal phase of SnO2 in the composite. The scanning electron microscopic images
suggested the porous and relatively smooth surface of the composite, and transmittance electron microscopic
images showed the trapping of nano-cubes of Fe2O3–SnO2, having particles size in the range 95–185 nm, into the
organic framework of Black cumin seeds, whose zero point charge was found at pH 7.2. The composite was
investigated for adsorption of Methylene blue dye from water for which the results revealed that 2.0 gL-1 amount
of Fe2O3–SnO2/BC was sufficient to remove more than 95% dye, within 15 min, at 6–9 pH, from its 10 mgL−1
concentration. The thermodynamic studies established spontaneity, feasibility, and endothermic nature of the
adsorption process. The adsorption data was satisfactorily described by the Freundlich isotherm which indicated
inhomogeneous surface of the composite. Application of Temkin isotherm revealed the same extent of bonding
probability and heat of adsorption at 27, 35, and 45 °C. The free energy change calculated from Dubinin-
Radushkevich isotherm suggested weak interaction between Methylene blue and Fe2O3–SnO2/BC. The process
satisfactorily followed the pseudo-second order kinetics that was controlled by the film diffusion step which
indicated interaction of Methylene blue with functional sites of the Fe2O3–SnO2/BC. The Fourier-transform
infrared spectroscopy analysis gave the confirmatory evidence for interaction of Methylene blue to Fe2O3–SnO2/
BC. The maximum Langmuir adsorption capacity of the Fe2O3–SnO2/BC was found to be 58.82 mgg−1 at 27 °C
which is higher than the previously reported adsorbents, MnFe2O4/BC [J. Clean. Prod. 2018. 200, 996–1008],
and Fe2O3–ZrO2/BC [J. Clean. Prod. 2019. 223, 849–868]. Therefore, the study showed excellent results for
water treatment and can be useful to develop advance water treatment technology.

1. Introduction MB's direct contact with animals and humans can cause permanent
injury to the skin and eyes, and if inhaled through water can induce
Generation of coloured wastewater by textile and dyeing industries vomiting, nausea, inflammation of the stomach, diarrhea, delirium, and
host large amount of toxic organic dyes which are responsible for ser- excessive sweating (Bharti et al., 2019). Hejtmancik et al. (2002) have
ious water born deceases and other long term effects (Chauhan et al., concluded from their experiments that no observed adverse effects level
2019; Li et al., 2017; Mohamed et al., 2016; Siddiqui et al., 2018a-c; (NOAEL) for MB in rats was 25 mgkg−1. Therefore, immediate removal
Tara et al., 2019). Methylene blue (MB) is a worst water pollutant of MB dye from water using any suitable technique is necessary for
whose presence in discharged water destroys the aesthetic quality of securing the human beings from adverse health effects. However, re-
water by imparting dark blue coloration which inhibits the sunlight moval of dyes through adsorption is the only low energy consuming,
penetration into the water, absorbs dissolved oxygen, and affects and convenient technique which needs easy instrumentation with
human health adversely (Bharti et al., 2019; Kataria and Garg, 2019). nominal cost (Dong et al., 2019; Kim et al., 2017; Zare et al., 2018).


Corresponding author.
E-mail address: saifchaudhry09@gmail.com (S.A. Chaudhry).

https://doi.org/10.1016/j.envres.2019.108667
Received 27 March 2019; Received in revised form 12 August 2019; Accepted 13 August 2019
Available online 16 August 2019
0013-9351/ © 2019 Elsevier Inc. All rights reserved.
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667

Commercial activated carbons have previously been studied the most as chromium, cobalt, copper, manganese, tin, titanium, and zirconium etc.
highly porous adsorbents and are largely employed in water treatment (Siddiqui and Chaudhry, 2017a, 2017b). Each component in the re-
but unfortunately their performance is poor for certain target func- sulting binary oxides has its unique and special properties which ad-
tionalities (Giannakoudakis et al., 2016; Vikrant et al., 2019a,b). vances its behaviour in comparison to the individual monometallic
The water cleaning potential of few other solid materials has opened oxides, and thus has shown remarkable enhancement in its adsorption
hopes, and has motivated the researchers to make the process more capacity. Natural carbon-based framework materials derived from
convenient and efficient by developing new and advance adsorbents plants can be more convenient than activated carbon and other organic
with low-cost (Ghorai et al., 2014; Hosseinzadeh and Mohammadi, moieties (Ezechi et al., 2015; Guler et al., 2016). The plant-based fra-
2015; Nanda et al., 2016). The solids which have higher adsorption mework, however, can release organic contents during adsorption
sites (functional groups) available at the surface can have higher process which may change the physical qualities of treated water like
binding efficiency towards charged pollutants, therefore, various solids odour and taste. But fortunately, the combining carbon framework with
have been modified (Siddiqui and Chaudhry, 2017a-d). inorganic part enhances chemical, mechanical, and thermal stabilities
Basaleh et al. (2019) has modified vermiculite, a clay mineral, with of resulting materials (Chen et al., 2017; Siddiqui et al., 2017). Fur-
polyamide through in-situ interfacial polymerization, to develop low- thermore, if parts of the plants are chosen which have medicinal and
cost polyamide-vermiculite nanocomposite for Methylene blue cleaning anti microbial properties then the material can be more beneficial
from water. The modified vermiculite showed 76.42 mgg−1 Langmuir (Siddiqui and Chaudhry, 2019). However, the stable bonding between
adsorption capacity which was better than that of unmodified vermi- the nanoparticles and organic framework is still far from the achieve-
culite. He et al. (2019) modified Polydopamine (PDA)-coated kaolin ment of stable composite, thus during the adsorption process, compo-
with reduced graphene oxide, PDA-rGO-kaolin, for the removal of sites may release nanoparticles and can cause toxicity in water on long
Methylene blue from water. The surface area of a solid material is one term accumulation (Siddiqui and Chaudhry, 2019).
of primary criterion for the selection of an adsorbent and materials with Keeping these merits and demerits of previously reported adsorptive
higher surface area show higher adsorption efficiency for pollutants in materials in mind, the iron-tin binary oxide nanoparticles, Fe2O3–SnO2,
water. The BET surface area analysis for PDA-rGO-kaolin has shown were incorporated into the carbon framework of Nigella sativa seeds
that the surface area of PDA-kaolin increased by 3.1 times on the in- (black cumin), in order to achieve the low-cost, chemically, thermally
corporation of rGO into PDA-kaolin, hence, the reported 39.66 mgg−1 and mechanically stable, and environmentally sustainable, material for
adsorption capacity for MB which was much higher than PDA-kaolin. dye remediation. The choice of Black cumin seed, BC, is a promising
Thus, the introduction of organic framework to the solid can improve selection due to its worldwide availability, lower cost, nontoxic,
the adsorption performance of the material. availabilities large functional groups, biocompatible, and medicinal
Among various types of modified materials, the metal-organic fra- nature (Bingol et al., 2012; Singh et al., 2005). Nontoxic-BC seeds have
meworks, MOFs, are most prominent engineered adsorbents (Siddiqui pleasant spicy smell and pungent taste, and well known for their mir-
et al., 2019b, 2019c, 2019a, 2019d). Arora et al. (2019) have developed aculous therapeutic activities (Iqbal et al., 2017; Muhtasib et al., 2006).
iron-based metal organic framework by introducing iron metal into the Therefore, the use of these seeds can be efficient for water treatment
organic framework of benzene dicarboxilic acid. The developed, iron- without imposed toxicity, and any changes in the quality of water.
based MOF was utilized for the removal of MB from water to remove Recently these seeds have been utilized for adsorptive removal of pol-
94.74% of MB from 5 mgL−1 concentrated dye solution after 24 h, lutants from water (Ahmad and Haseeb, 2015; Siddiqui et al., 2018a,
using 25 mg of MOF. Lozano et al. (2018) fabricated zirconium-based 2018b).
MOF, UiO-66, having structure which consist of three dimensional The efficiency of MOF-based adsorbents has been reported markedly
cluster of zirconium atoms connected to each other by benzenedi- improved in comparison to the naked ones (Siddiqui et al., 2019b) .
carboxylate, for MB dye removal. Yang et al. (2018) have reported the Thus the aim of incorporation of Fe2O3–SnO2 into BC framework was to
doping of cerium into the UiO-66 to develop Ce(III)-doped UiO-66 develop high efficiency material for water treatment. Fe2O3–SnO2 na-
nanocrystals which showed 490% exceeded MB adsorption than UiO- noparticles have been used but hardly any reference is available in the
66. The zeta potential and isotherms studies suggested that the higher literature where these particles have been incorporated into the natural
MB adsorption capacity of Ce(III)-doped UiO-66 might be attributed to plant seed-based framework. Therefore, the objective of the present
the enhanced adsorption sites on the surface of UiO-66 on Ce(III) work, preparation of Fe2O3–SnO2 incorporated BC, Fe2O3–SnO2/BC
doping which ultimately promoted π-π interactions between Ce(III)- nanocomposite, is a novel approach towards the advance water treat-
doped UiO-66 and MB. Carboxylated ethylenediamine functionalized ment technology.
Fe3O4@SiO2 nanoparticles, Fe3O4@SiO2-EDA-COOH NPs, was also ex- The prepared Fe2O3–SnO2/BC nanocomposite was investigated for
plored for the MB removal from water, and showed the higher MB MB adsorption from aqueous medium and its efficiency has been
adsorption capacity than several other adsorbents (Jiaqi et al., 2019). compared to the previously reported adsorbents. The experiments were
Although, these were the best examples of current advancements in carried out to optimize various experimental parameters viz.
the adsorption technique but still the fewer adsorption sites on the Fe2O3–SnO2/BC dosage, reaction temperature, solution concentration,
surface and toxicity associated with adsorbent are most concerning is- and pH. The collected adsorption data was verified with various iso-
sues. Therefore, the search for health-friendly organic frameworks and therms to understand the interaction of MB and Fe2O3–SnO2/BC. The
inorganic particle is needed for enhancement of adsorption sites and to kinetic data was tested by applying in various kinetic equations and the
reduce the toxicity of an adsorbent simultaneously. Biocompatible spontaneity and feasibility of the process was determined by putting the
cellulosic surface with high functionalities can be a good choice for temperature dependant adsorption data to the thermodynamic equa-
organic frameworks and simultaneous doping of oxide particles with tions. The mechanism of MB adsorption has also been discussed herein
other metals for inorganic particle (Cao et al., 2018; Rahmi and with the help of application of various mathematical relationships and
Mustafa, 2019). parameters derived from them as well as Fourier-transform infrared
Synthetic metal oxides such as Al2O3 (Malakootian et al., 2015), spectroscopy analysis.
CeO2 (Yari et al., 2015), CuO/Cu2O (Chauhan et al., 2019), Fe2O3/
Fe3O4 (Stan et al., 2017), TiO2 (Badawy et al., 2015), SnO/SnO2 (Al- 2. Experiments
Hamdi et al., 2017), and ZnO (Ong et al., 2016; Zaidi et al., 2019) etc.
have been utilized as adsorbents. Among these Fe2O3 or Fe3O4 have 2.1. Materials and methods
been studied extensively due to their non-toxic behaviour but have
limited capacities which can be increased by doping metals like Precursor salts, SnCl2 and FeCl3, used for the preparation of

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S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667

Fe2O3–SnO2/BC, and HCl and NaOH required for pH adjustment were determined using ultraviolet–visible (UV–Vis) spectrophotometer
purchased from Merck India ltd., New Delhi; Methylene blue (Mw. (model T80-UV/VIS, by PG Instruments Ltd., Leicestershire, England).
319.85 gmol-1, λmax 660 nm was procured from Sigma-Aldrich India All the samples were centrifuged prior to analysis by the UV–Vis
ltd., New Delhi. Nigella sativa (Black cumin) seeds were purchased spectrophotometer at λmax 660 nm as reported in literature (Bentahar
from local market, near Jamia Millia Islamia, New Delhi. et al., 2017). Type 5UV10 (Square) UV quartz cuvette of 10 mm path
length with 4.5 mL volume was used for spectrophotometric measure-
2.2. Preparation of dye solutions ments. The volume of the samples taken for spectrophotometric mea-
surements was 3.5 mL and difference in concentration of MB solution
The dye stock solution of 1000 mgL−1 concentration was prepared before and after experiments gave the adsorption efficiency of used
by dissolving 1.0 g MB dye in 1 L of distilled water which was diluted to Fe2O3–SnO2/BC for MB using following equations (Chaudhry et al.,
required concentrations using dilution law before each experiment. 2017):
V
2.3. Preparation of Fe2O3–SnO2/BC nanocomposite Adsorption capacity, Qe = (Co − Ce )
(1)
m

The binary oxide, Fe2O3–SnO2, was incorporated into the BC carbon C − Ce ⎞


Percentage adsorption = ⎛ o
⎜ 100

framework following one step co-precipitation reaction. In brief, 1.0 g
⎝ Co ⎠ (2)
washed, dried, and powdered BC grains of size 60/200 mesh was so-
nicated in 100 mL water, then 100 mL each of 0.1M FeCl3 and 0.05M where Co, and Ce are initial and equilibrium concentrations of MB, re-
SnCl2 was added to the sonicated BC suspension under continuous spectively. V (L) is the volume of aqueous solution and m (g) is the
stirring for 20 min at 60 °C. Later, pH of the mixture was adjusted to dosage of Fe2O3–SnO2/BC.
10.5 by dropwise addition of 8M NaOH solution under continuous
stirring condition, which gave the brownish precipitate of nano- 2.6. Reusability test of Fe2O3–SnO2/BC
composite, Fe2O3–SnO2/BC. The reaction mixture was further stirred
for 15 min, and thus resultant precipitate was cooled to room tem- The reusability of used adsorbent is one of the most important
perature, and then filtered, washed repeatedly with distilled water, and parameter to achieve suitable and efficient water treatment technology.
dried for 48 h at 65 °C. The prepared composite, Fe2O3–SnO2/BC, was The reusability of adsorbent also reduces the cost of overall process and
characterized for the confirmation of synthesis/formation and in- makes the process effective for long term. The reusability of any pol-
corporation of binary oxide into the BC framework. The functional sites lutants loaded adsorbent can be achieved by desorption of pollutants
at the surface, zero point charge of the surface, particle size, mor- from adsorbent surface and thus the achieved adsorbent is known to be
phology, elemental composition, and thermal stability of Fe2O3–SnO2/ as regenerated adsorbent. Regenerated adsorbent can be used for fur-
BC were ascertained by employing several spectroscopic and micro- ther cycle and this process repeated for several adsorption-desorption
scopic techniques (Chaudhry et al., 2016). cycles depends on the reusability of adsorbent. This gives an appro-
priate knowledge of quality of generated adsorbent for particular pol-
2.4. Determination of zero point charge lutant. For this study, certain amount of Methylene blue loaded
Fe2O3–SnO2/BC was shaken with the 0.1M of acidic (HCl) solution in
The pH point at which solid surface get neutralized is known as 100 mL Erlenmeyer flask on water bath shaker for 6 h at 27 °C.
point of zero charge (PZC) or zero point charge (ZPC) of the solid and Afterwards the regenerated Fe2O3–SnO2/BC was centrifuged, washed
regulates the trend of the adsorption of pollutants on changing pH of an till neutral pH and dried, and then reused for further rounds of MB
aqueous solution. The salt addition method, one among various avail- adsorption.
able methods, was used to calculate ZPC of the prepared Fe2O3–SnO2/
BC using a series of 100 mL Erlenmeyer flasks containing 10 mL of 3. Result and discussion
0.01M KNO3 solution with initial pH 2–10 (Muhammad et al., 2012).
200 mg of the prepared Fe2O3–SnO2/BC was added to each flask and 3.1. Preparation and characterization
then stirred in water bath shaker for 24 h at room temperature. After
24 h, pH of the each mixture was measured using pH meter (Model APX The Nigella sativa seed (BC) have several functional groups which
175 E/C by Control dynamics instrumentation Pvt. Ltd., Bangalore, can hold Fe2O3–SnO2 nanoparticles through M-OH and BC-OH inter-
India). The initial and final pH values were used to calculate the ZPC of actions. The electrostatic and hydrogen bonding interactions between
the prepared composite by plotting the graph. BC and Fe2O3–SnO2 nanoparticles kept them tied to each other and thus
produced a mechanically strong product that did not release
2.5. Batch adsorption studies Fe2O3–SnO2 nanoparticles in water during the adsorption process. The
growth of Fe2O3–SnO2 nanoparticles into the BC framework was con-
The optimum MB removal efficiency of the prepared Fe2O3–SnO2/ firmed from FT-IR spectrum of the prepared Fe2O3–SnO2/BC (Fig. 1b).
BC was examined by varying the amount of Fe2O3–SnO2/BC, con- The IR absorption study of BC had been carried out previously
centration, and pH of MB solution. All the experiments were carried out (Siddiqui and Chaudhry, 2019) which established stretching vibrations
in batch manner by agitating the series of 100 mL Erlenmeyer flasks corresponding to -O-H, -C-H of –CH3, and –CH2, –C]O of carboxyl, C]
having 10 mL MB solution of 10 mgL−1 concentrations and certain O of amide, N–H of amide, –C]C-, C–O, and -O-H of –COOH at certain
amount of Fe2O3–SnO2/BC, for 120 min, at pH 7.0, 27 °C and 200 rpm frequencies. For this study, the infrared spectrum of bare Fe2O3–SnO2
shaking speed. Thermodynamic, and isotherm parameters were de- showed the absorption bands corresponding to the stretching and
termined by varying the concentration of MB from 10 to 60 mgL−1 at bending modes of hydroxyl groups as well as M-O- vibrations. The
27, 35, and 45 °C using optimum dosage of Fe2O3–SnO2/BC, at pH 7.0, absorption peak in the range 3550–3412 and 1633 cm−1 indicated the
and 200 rpm shaking speed for 120 min reaction time. Contact time presence of –OH i.e. M-OH groups at the surface of Fe2O3–SnO2 nano-
effect and kinetic parameters were investigated, for 10 mL of MB so- particles and confirmed the hydrated surface of binary oxide. The ab-
lution of 10 mgL−1 concentration, by changing the reaction time sorption bands at 606 and 493 cm−1 were assigned to the metal-oxygen
(15–120 min) using optimum dosage of Fe2O3–SnO2/BC, at 27 °C and vibrational frequencies of Fe2O3–SnO2 (Chaudhry et al., 2016; Li et al.,
200 rpm shaking speed. 2016; Subramaniasiva et al., 2009) (Fig. 1a). Above absorption bands
The concentration of MB in the solution after each experiment was affirmed the presence of –OH groups on the BC as well as binary oxide

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nanoparticles and formation of the metal-oxygen (M-O) bonds with BC


surface. In addition to interaction between the BC and bare nano-
particles, the FT-IR spectrum also showed large number functional
groups present on the surface of the prepared composite which might
had been utilized for MB adsorption from aqueous solution. The FT-IR
spectrum of the composite were assigned broad peak for stretching
vibrations of -O-H at around 3231 cm−1 and two absorption bands for
C–H stretching of –CH3 and –CH2 in between the 2850-2930 cm−1. The
peaks for –C]O of ketonic group, –C]O and N–H for amide groups
was also assigned for the prepared material. Peaks at 1701, 1598, and
1528 cm−1 were attributed to the –C]O of carboxyl, –C]O, N–H of
amide groups, respectively. The IR stretching frequency at 1452, 1390,
and 1244 cm−1 was assigned for the –C]C-, -C-O, and -O-H of –COOH,
respectively. The absorption peaks at 584 and 495 cm−1 were attrib-
uted to the vibrational frequencies of M-O bonds of Fe2O3–SnO2. All
these peaks were also confirmed from the previous literatures (Siddiqui
and Chaudhry, 2019).
The crystal phases of the prepared Fe2O3–SnO2/BC were char-
acterized from X-ray diffraction pattern. The previously published lit-
erature (Siddiqui et al., 2019b) reported that the XRD patterns of the BC
showed the broad peak in the range 20–25° (2θ) for cellulosic surface.
The XRD spectrum of Fe2O3–SnO2/BC (Fig. 2) showed the diffraction
peaks due to Fe2O3 as well as SnO2 at various 2θ values. The diffraction
peaks at around 30, 35, 43, 53, and 63° (2θ) corresponding to (220),
(311), (400), (422), and (440) planes, respectively, might be due to the
crystals of either magnetite, Fe3O4, or maghemite, γ-Fe2O3. The crystal
lattice parameters of these phases are very close, therefore, it is difficult
to differentiate these structures, however, it has been reported in lit-
Fig. 1. FT-IR spectrum of (a) Fe2O3–SnO2 (b) Fe2O3–SnO2/BC.
eratures that the peaks corresponding to the (210) crystal plane is as-
sociated with the γ-Fe2O3 structure (Baltazar et al., 2015; Girod et al.,
2015). There is an existence of the peaks at around 23° (2θ) which
nanoparticles surfaces. These two could tightly interact with each other corresponded to the (210) plane, therefore γ-Fe2O3 can be confirmed in
through electrostatic and hydrogen bonding interactions between the the composite. In order to further confirming the actual phase of iron
hydroxyl functional groups on these two and formed the composite oxide in the composite a peak corresponding to the (311) plane was also
(Wang et al., 2016) (Scheme 1). The formation of Fe2O3–SnO2 into the examined. According to previously published literature (Shan et al.,
framework of BC was confirmed from the IR absorption bands of pre- 2007), the standard value of 2θ for (311) plane for Fe3O4 is 35.423°,
pared sample (Fig. 1b) which exhibited peaks corresponding to pure and 35.631° for γ-Fe2O3. For this study the 2θ value for (311) plane
seed powder, as reported in our previous study (Siddiqui and Chaudhry, appeared at 35.60° which is close to the standard value of γ-Fe2O3,
2019) as well as bare nanoparticles. However, the intensity of peaks therefore, the XRD pattern of the composite corresponded to the planes
attributed to the functional groups for virgin seed powder as well as of the cube of γ-Fe2O3 and matched well with JCPDS card no 39–1346.
nanoparticles weakened and some of which disappeared. The weak- These XRD patterns are in agreement with our previous works (Siddiqui
ening and disappearance of the peaks corresponding to BC and bare and Chaudhry, 2019). The XRD analysis also supports the presence of
nanoparticles indicated the strong interactions between BC and SnO2 particles onto the composite surface which were in good

Scheme 1. Schematic diagram of preparation and inset of Fe2O3–SnO2/BC.

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S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667

Fig. 2. XRD pattern of (black) Fe2O3–SnO2 and (red) Fe2O3–SnO2/BC. (For


interpretation of the references to colour in this figure legend, the reader is
referred to the Web version of this article.)

accordance with the (110), (101), (200), and (301) crystal planes of
tetragonal phase SnO2 (JCPDS card no. 41–1445) (Gu et al., 2017). The
peak intensities of BC, and γ-Fe2O3, and SnO2 in the nanocomposite got
reduced which strongly proved the interaction between the nano-
particles and BC (Rahman et al., 2013). This showed that BC surface
Fig. 3. SEM image of (a) BC and (b) Fe2O3–SnO2/BC.
hold the Fe2O3–SnO2 nanoparticles that were formed in its framework.
The average size of crystal was calculated to be 56.90 nm using Debye-
Scherer equation being given below: no significant change in adsorption percentage was observed. Hence,
2.0 gL-1 amount of Fe2O3–SnO2/BC was selected as optimum dose for

D= further studies.
βCosθ (3)
The investigations of effect of contact time (15–120 min) have
where λ is wave length of the X-ray radiation (λ = 0.154 nm), θ is suggested that the adsorption of MB onto Fe2O3–SnO2/BC occurred in
Bragg's angle, and β is the full width at half maxima. two phases, initial fast phase and later slow. During the initial phase an
The SEM images (Fig. 3) of the prepared Fe2O3–SnO2/BC suggested instantaneous adsorption was observed, and in the later stage the ad-
the porous and relatively smooth nature of the composite, composed of sorption slowed down. The 95% adsorption was observed initially
large-scale, heterogeneous, and coarse crystals. The nano-cubes of within 15 min and then the process slowed down and slightly increased
Fe2O3–SnO2 of the sizes ranging from 95 to 185 nm were also in- to 97.5% on prolong the contact time from 15 to 75 min, and almost
vestigated by TEM scanning (Fig. 4a). The TEM images also clearly stopped at 90 min [Fig. S3; Supplementary Information]. This happened
showed how the prepared cubic nanoparticles were trapped into the BC because after certain period of time, the pores and the functional sites
framework, in great extent, although some partially cubic particles on Fe2O3–SnO2/BC might have been filled and occupied thus MB mo-
were also present. lecule needed specific way to find the target and thus the rate becomes
The selected area electron diffraction (SAED) pattern showed the slower.
XRD rings (Fig. 4b) which corresponded to the presence of crystalline
particles of nanocubes of γ-Fe2O3 and tetragonal phase SnO2 in the 3.2.2. Effect of solution pH
composite (Zhu et al., 2011). pH range 2.0–10 was chosen for studying the pH effect on MB ad-
The estimated zero point charge of the surface of the prepared sorption in similar conditions (2.0 gL-1 amount of Fe2O3–SnO2/BC,
Fe2O3–SnO2/BC, using salt addition method (Muhammad et al., 2012), 10 mL MB solution of 10 mgL−1 concentration, contact time 120 min
was at pH 7.2 [Fig. S1; Supplementary Information] which was helpful and temperature 27 °C). The results are displayed in [Fig. S4; Supple-
for understanding the adsorption tends under the influence of solution mentary Information]. At low pH the excessive protonation generated
pH. positive charge on the surface of Fe2O3–SnO2/BC which decreased the
adsorption of positively charged MB ions till pH 7.25. Moreover, there
3.2. Batch adsorption study may be competition between H3O+ and MB for binding site at lower pH
which results into a decrease of MB adsorption for Fe2O3–SnO2/BC.
3.2.1. Effect of adsorbent dose and reaction time However, when the pH increased the OH− ions concentration increased
Four different amounts of Fe2O3–SnO2/BC, ranging from 1.0 to 4.0 due to addition of base, and the surface become negatively charged and
gL-1, in 10 mL solution having 10 mg−L1 MB concentration, were used attraction of MB+ to Fe2O3–SnO2/BC increased. The pHzpc of
to test the effect of Fe2O3–SnO2/BC dosage on the adsorption capacity. Fe2O3–SnO2/BC was 7.25 below which the surface was positively
The significant variation in the adsorption efficiency of the charged and electrostatic attraction was low and that slowed the MB
Fe2O3–SnO2/BC was observed at different dosage [Fig. S2; Supple- adsorption. Above pHzpc the Fe2O3–SnO2/BC surface was negatively
mentary Information]. The variation trend showed that the adsorption charged, that increased the force of attraction for cationic MB, and
capacity increased from 94 to 98% with the increase in the amount of adsorption increased. Therefore, 6–10 was suitable pH for MB sorption
Fe2O3–SnO2/BC from 1.0 to 2.0 gL-1 but on increasing the dose further, onto Fe2O3–SnO2/BC.

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S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667

Fig. 4. a. TEM images of Fe2O3–SnO2/BC at different magnifications. b. SAED pattern of Fe2O3–SnO2/BC.

3.2.3. Thermodynamics values of ΔH° and ΔS°, respectively [Fig. S5; Supplementary Informa-
The sorption of MB from water to solid surface can be more easily tion]. ΔS° value reflects the affinity of Fe2O3–SnO2/BC towards MB and
understood from the thermodynamic parameters which include free the sign of ΔH° gives indication about the nature of process, either
energy change, ΔG°, enthalpy change, ΔH°, and entropy change, ΔS°. endothermic (+Ve) or exothermic (-Ve) (Chaudhry et al., 2016).
The indication sign of these thermodynamics parameters are used for For the present study, thermodynamic parameters were determined
checking the heat change during sorption, either exothermic or en- by performing the batch experiments for 120 min at pH 7.0, and
dothermic, spontaneity and feasibility of the adsorption phenomenon. 200 rpm shaking speed, using constant adsorbent dose, 2.0 gL-1, by
Generally, the rise in the temperature during adsorption process, varying the concentration of MB from 10 to 60 mgL−1 at 27, 35, and
showed improved kinetics, hence gives the more negative, -ΔG° values 45 °C.
which is a sign of spontaneous adsorption and effective of electrostatic The negative values of ΔG° (−6.495, −24.077 and −26.790 kJmol-
1
interaction between adsorption sites and solute molecules(Siddiqui and ) confirmed the feasibility and spontaneity of the process at 27, 35, and
Chaudhry, 2018a,b). ΔH° and ΔS° are the determination factors of ΔG° 45 °C, respectively. The higher negative value of ΔG° at elevated tem-
of the process. perature indicated higher spontaneity and affinity of electrostatic in-
These variables were evaluated from the Langmuir constants, b, by teraction between MB and the Fe2O3–SnO2/BC at 45 °C. Thus, the MB
using given equation (Chaudhry et al., 2016): sorption onto the Fe2O3–SnO2/BC was endothermic in nature which
could be justified from the observed positive value of ΔH° +30.34
ΔGo = −RT ln b (4)
kJmol-1. However, the magnitude of ΔH° less than 80 kJmol-1 also
On substituting for ΔG° in the Van't Hoff equation we get: supported the weak interaction of MB onto Fe2O3–SnO2/BC surface.
Moreover, during the adsorption the ΔS° value was found to be nega-
ΔGo ΔS o ΔH o tive, −0.103 kJmol−1K−1, which suggested declined level of degree of
= −
RT R RT (5) freedom at solid-liquid interface. The similar observation had been
The slope and the intercept of the plot ΔG°/RT against 1/T give the made from isotherm studies.

6
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667

3.2.4. Isotherms modelling


The isotherm investigation gives the knowledge of distribution way
of pollutant between the solid and aqueous phases. The surface prop-
erties, affinities of the adsorbent towards adsorbate, adsorption capa-
cities, and involved mechanism were evaluated from the isotherm ex-
periments carried out at 27, 35 and 45 °C by varying the concentration
of MB between 10 and 60 mgL−1 with 2.0 gL-1 adsorbent dosage at
other optimum conditions [Fig. S6; Supplementary Information]. The
obtained equilibrium data was substituted into the linear forms of
Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms
(Siddiqui et al., 2018a).

3.2.4.1. Langmuir isotherm. Langmuir isotherm parameters display


interactive relationship of adsorbate to the adsorption sites at
equilibrium. The derivation of the Langmuir isotherm is based on the
assumption that maximum adsorption capacity corresponds to the
weight of adsorbate which form monolayer on the unit weight of the
adsorbent. This isotherm, is applied to those systems where exist
energetically equivalent adsorption sites and ions bind chemically to
them without lateral interaction. The linearized mathematical form of
Langmuir isotherm is given as (Siddiqui and Chaudhry, 2018a,b):
Ce C 1
= e +
Qe Qo Qo b (6)
−1
where Qo (mgg ) is weight of the adsorbate that can be adsorb by a
unit mass of the adsorbent for the formation of monolayer on the solid
surface and is called adsorption capacity. b (Lmg−1) is Langmuir
constant, that is related to the affinity of adsorbent for the adsorbate.
For the present case, the Ce/Qe vs Ce plots at 27, 35 and 45 °C (Fig. 5a)
gave Qo and b values from the slope and the intercept, respectively, and
are given in Table 1. An equilibrium parameter (RL), called separation
factor, was also calculated from the b values using following
relationship:
1
RL =
(1 + bCe ) (7)

RL value indicates the shape of isotherm or reversibility of the


process. For irreversible adsorption, RL = 0, for unfavorable adsorption
RL > 1, for linear RL = 1; and for favourable adsorption 0 < RL < 1
(Chaudhry et al., 2016).
The maximum Langmuir adsorption capacity was found to be in
increasing order in range 58.82–84.74 mgg−1 (Table 1) at the tem-
perature range 27–45 °C which indicated the endothermic nature of MB
adsorption process, but this observation is not as per the effect of
temperature on adsorption where adsorption decreased with increase in
adsorption. Moreover, the Langmuir constant (b) decreased from 0.772
to 0.368 Lmg−1 when the temperature of the adsorption system was
increased from 27 to 45 °C, which suggested the lower heat of adsorp-
tion or lower affinity of MB towards Fe2O3–SnO2/BC at higher tem-
perature. However, the RL value in the range 0–1 indicated that the
sorption process was favourable. The value of regression coefficient
(R2) of Langmuir isotherm was averagely 0.94 which indicated rela-
tively poor fitting of the data to Langmuir isotherm.

3.2.4.2. Freundlich isotherm. Freundlich isotherm, used to explain


adsorption phenomenon on energetically heterogeneous surface at
which ions bind physically and form multilayer with lateral
interactions. This isotherm is based on assumption that solids have a
numbers of adsorption sites, each with specific energy; and overall
surface is heterogeneous. The stronger adsorption sites are occupied
first, and adsorption energy decreases exponentially upon the Fig. 5. a. Langmuir isotherm plots for MB adsorption. b. Freundlich isotherm
plots for MB adsorption. Fig. 5c. Dubinin-Radushkevich isotherm plots for MB
completion of the process. The linear forms of Freundlich isotherm
adsorption.
can be expressed by the relationship (Chaudhry et al., 2016):
1
log Qe = log kF + log Ce
n (8)

7
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667

Table 1
Isotherm parameters for the adsorption of MB onto Fe2O3–SnO2/BC.
Temp. (°C) Langmuir Freundlich Temkin Dubinin-Radushkevich

−1 −1 −1 −1
Qo (mgg ) b (Lmg ) RL R 2
kF ( n R 2
AT (Lg ) BT (kJmol ) R 2
QD-R (mgg−1) β (mol2kJ−2) E (kJmol−1) R2
mg(1−n) Lng−1)

27 58.82 0.77 0.11 0.92 15.49 1.36 1.00 0.123 1.90 0.93 23.57 −0.0009 23.57 0.89
35 90.09 0.39 0.20 0.94 13.80 1.18 0.99 0.124 1.97 0.93 25.69 −0.001 19.61 0.94
45 84.74 0.37 0.21 0.95 12.58 1.18 0.99 0.125 2.05 0.93 25.30 −0.002 18.26 0.93

where kF and n are Freundlich constants which represent adsorption where T is temperature in Kelvin scale. The results obtained from the
capacity at unit concentration and intensity of adsorption, respectively. above equations (Fig. 5c) at temperature range 27–45 °C are depicted in
For favourable adsorption, n values should be in the range of 1–10, and Table 1. The QD-R values were found to slightly increase in the range
confirm the heterogeneity of the surface, and the value below 1.0 23.57–25.30 mgg−1 which once more time confirmed the endothermic
means the adsorbate is difficult to adsorb by adsorbent. These constants nature of the current process. β value was found to be lowest (−0.0009
were calculated from the intercept and the slope of plots of logQе versus mol2J-2) at 27 °C which revealed that the process was most feasible at
logCе (Fig. 5b). For the present case, the n values, in the range 1–10, this temperature. The β values were also applied to the following
indicated the favourable nature of the adsorption of MB on the relationship to determine the free energy change (ED-R) (Chaudhry
Fe2O3–SnO2/BC surface. The values of kF decreased slightly from et al., 2016):
15.48 to 12.58 mg(1−n)Lng−1 with increase in temperature from 27 to
ED − R = (−2β )−0.5 (12)
45 °C, indicating low adsorption capacity at elevated temperature
which conformed the observation from the effect of temperature on The calculated values of ED-R were found to be in range 23.57 to
the adsorption. Moreover, the unity or nearly unity R2 value at 27–45 °C 18.26 kJmol-1 (above, 8.0 kJmol-1) which confirmed the chemical in-
indicated better fitting of the adsorption data to Freundlich isotherm, teraction of MB ions to specific groups at Fe2O3–SnO2/BC surface
which suggested that the surface of Fe2O3–SnO2/BC should be (Siddiqui et al., 2019b).
heterogeneous and adsorption might be a physical process. From these isotherm studies (Table 1) the adsorption of MB from
aqueous solution onto Fe2O3–SnO2/BC was satisfactorily described by
3.2.4.3. Temkin isotherm. Temkin isotherm is employed to describe the the Freundlich isotherm model (R2 was nearly unity); which indicated
loading of solute molecules from non-ideal aqueous solution to MB sorption at the heterogeneous surface of Fe2O3–SnO2/BC and that
heterogeneous surface of adsorbents. Isotherm also assumes the too can be confirmed from SEM and TEM images which clearly in-
decline in heat of adsorption due to solute-solid interaction with the dicated rough surface. The experimental data fitting in Freundlich
surface coverage. This isotherm can be illustrated by the linearized isotherm may be because of non-homogeneous distribution of ad-
form of mathematical relationship (Chaudhry et al., 2016): sorptive sites on the Fe2O3–SnO2/BC surface since the Freundlich iso-
therm is based on heterogeneity of surface.
RT ⎞ RT ⎞
Qe = ⎛ ⎜ ln AT + ⎛
⎟ ln Ce
⎜ ⎟

b
⎝ T⎠ ⎝ bT ⎠ (9)
3.2.5. Adsorption kinetics
where AT and bT coefficients are measure of maximum binding energy, Explanation of adsorption kinetics and mechanism are necessary for
and enthalpy of adsorption, respectively. Results obtained from plots designing a proper water treatment system. The mechanism can be
between Qe and lnCe indicated that no significant change was observed devised from the dynamic parameters (Siddiqui and Chaudhry, 2019).
in AT (0.123–0.125 Lg-1) and bT (1.90–2.05 kJmol-1) values at the The adsorption of solute from the aqueous phase to the solid surface
temperature range 27–45 °C [Fig. S7; Supplementary Information]. This occurs in many steps and the slowest of these regulate the whole pro-
deduced the same extent of bonding probability and heat of adsorption cess. Therefore, the pace of MB molecules transporting from solution to
at all process temperatures. Positive and less than 8.0 kJmol-1 values of the surface of Fe2O3–SnO2/BC determined the kinetics of the adsorp-
bT indicated the endothermic nature of the MB adsorption onto tion. Six different kinetic models, i.e., the pseudo-first order (PFO), the
Fe2O3–SnO2/BC surface through weak interaction between MB and pseudo-second order (PSO), Elovich, intraparticle diffusion, film diffu-
Fe2O3–SnO2/BC. sion models and Boyd law, were applied for describing the present
adsorption system. For calculating the kinetic parameters batch ex-
3.2.4.4. Dubinin-Radushkevich isotherm. The Dubinin-Radushkevich (D- periments were performed for 10 mL of MB solution of 10 mgL−1
R) isotherm was also used to confirm the nature of the MB sorption onto concentration by changing the reaction time by 15–120 min, using
Fe2O3–SnO2/BC as discussed in the earlier report (Chaudhry et al., constant adsorbent dose, 2.0 gL-1, at 27 °C and 200 rpm shaking speed,
2016). This model is generally applied to the adsorption systems having and the obtained data was fitted to the above said kinetics models.
high or intermediate concentrations, to understand the adsorption
mechanism with respect to Gaussian energy distribution onto the 3.2.5.1. Pseudo-first order kinetics. Pseudo-first order, PFO kinetic
heterogeneous adsorption sites. The physisorption or chemisorption model has been introduced by Lagergren and modified by Ho. PFO is
nature of ions can also be distinguished by calculating the free energy, based on the assumption that rate of absorption depends only on
ED-R, from D-R isotherm (Dabrowski, 2001; Dubinin, 1960), the available adsorption sites on the solid surface and can be expressed as
linearized form of which is given by the following expression: (Siddiqui and Chaudhry, 2019):

ln Qe = ln QD − R − βε 2 (10) k1
log(Qe − Qt ) = log Qe − t
2.303 (13)
where QD-R (mgg−1) is monolayer saturation capacity, β (mol2J−2) is
−1 −1
the mean free energy of adsorption and ε, the Polyani potential, was where k1 (min ) is PFO rate constant, and Qt (mgg ) is the
calculated following the relationship (Chaudhry et al., 2017): adsorption capacity at time t. The plot of log(Qe-Qt) as a function of t
[Fig. S8; Supplementary Information] gives the PFO parameters.
1⎞
ε = RT ln ⎛1 +⎜ ⎟

⎝ Ce⎠ (11) 3.2.5.2. Pseudo-second order kinetics. Pseudo second order, PSO kinetic

8
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667

model is applied to those systems where sorption rate is controlled by clearly indicated the interaction between MB and appropriate func-
the available adsorptive surface sites as well as solute molecules in the tional sites at the Fe2O3–SnO2/BC surface. The fitting of the experi-
liquid phase. The adsorption rate results from the difference between mental data to PSO relationship also indicated that the functional sites
the numbers of unoccupied adsorptive sites at equilibrium and total on the Fe2O3–SnO2/BC surface and MB ions in the liquid phase together
adsorptive sites on the adsorbent. The chemical interaction of solute to determine the rate of adsorption, thus showed more satisfactory result
the adsorption sites at the surface of an adsorbent is rate-limiting step for this adsorption study.
for PSO kinetic model being expressed in linear form as (Priyanka and The pace of liquid-solid adsorption process can depend on the sur-
Kumar, 2018): face adsorption, crossing of solute through boundary layer (film) and/
t 1 t or diffusion of solute into the interstitial parts of adsorbent. From above
= + time dependant results, the present adsorption process was rapid;
Qt h Qe (14)
therefore, MB kinetic data was applied to the intra-particle diffusion,
2
where h is initial rate constant that equals to k2Qe , and k2 IPD, and liquid-film diffusion models, LFD. Intra-particle diffusion
(gmg−1min−1) is the PSO rate constant. The plot of t/Qt against t model applies to those systems where chemical or physical bond is
gives [Fig. S9; Supplementary Information] these kinetic quantities. formed through diffusion of liquid phase adsorbate into the interior
The calculated regression coefficients and other quantities from these pores of adsorbent and this would be the rate determining step. This can
models determine the experimental adsorption data fitting. be explained by the Weber and Morris model which assume that solute
The regression coefficient (R2) and rate constant for PFO were ob- uptake varies proportionally with t0.5 and expressed as (Chaudhry et al.,
tained as 0.99 and 0.044 min−1, respectively, with theoretical value of 2017):
adsorption capacity Qe(cal) of 0.280 mgg−1 which was much lower than
Qt = kipd t 0.5 + C (16)
the experimental adsorption capacity value Qe(exp) of 4.90 mgg−1 for
MB dye. Therefore, PFO model did not explained the adsorption of MB where kipd is IPD rate constant that is equal to the slop of the plot of Qt
dye onto Fe2O3–SnO2/BC. versus t0.5. Intra-particle diffusion would be the rate determining steps
The PSO rate equation is based on idea that reaction rate depends on if the straight line plot passes through the origin otherwise film diffu-
the number of sites on the surface and the number of adsorbate ions in sion would be controlling the rate. The value of the intercept, C, ob-
water. The results obtained by fitting data to PSO equation are depicted tained for IPD plot suggests the partial controlling of rate by film dif-
in Table 2 which indicated that the adsorption data well fitted to the fusion step.
PSO kinetic equation. The value of regression coefficient (R2) of PSO Liquid Film diffusion model, LFD, applies to those systems where
plot was higher than PFO and also approached to unity. Furthermore, the crossing of liquid film generated around the solid surface, is a rate
the theoretical adsorption capacity, Qe(cal), of 4.92 mgg−1 for PSO was determining step in the process of adsorption of solute molecules onto
close to the actual adsorption capacity, Qe(Exp), of 4.90 mgg−1 observed the solid surface, which can be expressed as (Chaudhry et al., 2017):
during experiment at optimum contact time.
ln(1 − F ) = −kfd t (17)
3.2.5.3. Elovich kinetic model. The experimental MB adsorption data where F=Qt/Qe and kfd is film diffusion rate constant. If ln(1-F) versus t
was also examined by the Elovich kinetic model which is applied to plot is linear and passes through the origin then the process follows the
those liquid-solid adsorption systems where chemical interaction occurs LFD model.
between adsorbate and heterogeneous adsorbent, and no lateral From the IPD plot [Fig. S11; Supplementary Information], the kipd
interaction occurs. Earlier, Elovich model was used only for the gas- value was calculated as 0.0162 mgg−1min−0.5 and the intercept of the
solid adsorption system, however, these days it is widely being used for plot was found to be 4.73 with regression coefficient R2 = 0.93. The
liquid-solid adsorption system having interaction between the values determined from the IPD plot affirmed that IPD singly not con-
functional sites of adsorbent and adsorbate (Wu et al., 2009). This trolled the rate of adsorption.
model can be expressed as (Chaudhry et al., 2017): The straight line plot of ln(1-F) against t gave kfd as
1 1 −0.044 mgg−1min−1 [Fig. S12; Supplementary Information] with in-
Qt = ⎜⎛ ⎟⎞ ln(αβ ) + ⎜⎛ ⎟⎞ ln t tercept −2.87. The regression coefficient for straight line plot was
β
⎝ ⎠ ⎝β⎠ (15)
found to be 0.99, along with small intercept value which suggested that
where coefficients α and β represent the initial rate of adsorption and the kinetic data fitted to the film diffusion model. Therefore; film dif-
rate of desorption or activation energy required for the process [Fig. fusion might have controlled the kinetics of MB adsorption onto
S10; Supplementary Information]. Results (Table 2) suggested that α, Fe2O3–SnO2/BC surface.
7.286 × 1033 mgg−1min−1, is much higher value than β, The Boyd kinetic model was also applied for predicting rate con-
17.452 mgg−1, which suggested that MB adsorption rate was much trolling steps more accurately. This model, a combination of IPD and
higher than desorption which validates the higher adsorption on the LFD relationships, was given by Boyd et al. (1947) and mathematically
surface of Fe2O3–SnO2/BC. is expressed as follows:
From these equilibrium kinetic studies (Table 2), it has been eval-
Bt = −0.4977 − ln(1 − F ) (18)
uated that the adsorption of MB from aqueous solution onto applied
Fe2O3–SnO2/BC could satisfactorily be described by the PSO model on where Bt is a mathematical function of F=Qt/Qe and plot of Bt versus
the basis of R2 and nearly similar values of theoretical and experimental time t gives the characteristics evidence of either IPD or LFD steps. IPD
adsorption capacity of Fe2O3–SnO2/BC. The data fitting to PSO kinetics would be the rate determining step in case of Boyd linear plot passed

Table 2
Kinetic parameters for the adsorption of MB onto Fe2O3–SnO2/BC.
Pseudo-first order Pseudo-second order Elovich kinetic model Film diffusion model Intraparticle diffusion model
Qe(Exp) = 4.90 mgg−1 Qe(Exp) = 4.90 mgg−1

k1 ( Qe(cal) (mgg−1) R2 k2 Qe(cal) (mgg−1) R2 Α (mgg−1min−1) β (mgg−1) R2 kfd ( Inter kipd ( Inter
min−1) mgg−1 min−1) -cept R2 mgg−1min−0.5) -cept R2

0.044 0.280 0.98 0.0045 4.92 1 1.102 × 1033 17.452 0.98 −0.044 −2.87 0.99 0.016 4.73 0.93

9
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667

Moreover, hardly any significant change in the position of peaks cor-


responding to C–H groups was observed which indicated non-inter-
active behaviour of such group as expected. The whole explanation
indicated the adsorption affinity of various groups at the surface of
Fe2O3–SnO2/BC for MB (Scheme 2) (Siddiqui et al., 2019b).

3.2.7. Partition coefficient and comparative evaluation


The prepared Fe2O3–SnO2/BC showed higher maximum adsorption
capacity in comparison to several other adsorbents (Table 3b). This
might be due to small size of Fe2O3–SnO2 nanoparticles, heterogeneous
structure of Fe2O3–SnO2/BC, and large functional groups of BC. In
general, the performance of an adsorbent, for a particular pollutant, is
examined by comparing the maximum adsorption capacity of the ad-
sorbent to other reported adsorbents. However, this method is not ac-
curate because the maximum adsorption capacity is very sensitive to-
wards the operating conditions like pH, temperature of the system, and
concentration of pollutants etc. (Na et al., 2019; Szulejko et al., 2019;
Fig. 6. Boyd law plot for MB adsorption. Vikrant and Kim, 2019). Therefore, to assess the true performance of
the present material, the partition coefficient, PC, of Fe2O3–SnO2/BC
through the origin, otherwise boundary layer (film) crossing by ad- has been evaluated, which is the ratio of concentration of pollutants
sorbate formed around solid would be the rate determining step (Elkady adsorbed onto the solid surface and remained in the liquid phase at
et al., 2016). The present process might have controlled by the equilibrium. The partition coefficient (mgg−1μM−1) can be expressed
boundary layer (film) formation because the Boyd plot (Fig. 6) did not as (Vikrant and Kim, 2019; Vikrant et al., 2019a,b):
pass through the origin as intercept value was 2.373. This result can be PC = Adsorption capacity(Qe )/Final concentration (Ce ) (19)
considered as confirmatory result of fitting of kinetic data into the PSO
and film diffusion model. Therefore, from above kinetic results it can be PC = Adsorption capacity (Qe )/(Initial concentration (Co)⁎removal
strongly concluded that interaction between the functional sites of
rate (Qt )) (20)
Fe2O3–SnO2/BC and MB was responsible for the adsorption as predicted
from the D-R adsorption isotherm also. This could be further confirmed The prepared Fe2O3–SnO2/BC showed enhanced performance for
from the analysis of IR absorption peaks of MB loaded adsorbent. the adsorptive removal of MB from aqueous solution in terms of ad-
sorption capacity as well as partition coefficient under various experi-
3.2.6. Interaction of MB with Fe2O3–SnO2/BC mental conditions. The assessment of the performance of Fe2O3–SnO2/
As earlier suggested that MB adsorption kinetic followed the PSO BC under variation of MB concentration, adsorbent dose, reaction time,
kinetics meant the sites on the Fe2O3–SnO2/BC surface and MB ions in and temperature and MB solution pH requires estimation of partition
solution phase determined the mechanism of reaction that proceeded coefficients and adsorption capacities. The performance of
through the chemical interaction between MB and Fe2O3–SnO2/BC Fe2O3–SnO2/BC increased with the increase in concentration of MB
surface. Therefore, the functional behaviour of Fe2O3–SnO2/BC, struc- solution and the partition coefficient decreased (Fig. 8.). This was be-
ture of MB molecule, and interaction of dye to the adsorbent governed cause at higher MB concentration, the all sites at Fe2O3–SnO2/BC sur-
the mechanism of the process. The existence of large number of func- face might have got saturated, consequently, causing enhancement in
tional groups at the Fe2O3–SnO2/BC surface had been confirmed from the performance, and at this point the movement of MB ions might have
FT-IR spectrum. Due to presence of these groups, the Fe2O3–SnO2/BC been slowest and hence partition coefficient was lowest. As shown in
showed better uptake capacity than others reported adsorbents under Figs. 8 and 2.0 gL-1 dosage of Fe2O3–SnO2/BC displayed the best per-
similar conditions (Table 3b). The possible interaction between the formance in the terms of decrease in partition coefficient from 23.85 to
existing function sites on Fe2O3–SnO2/BC and MB can be easily un- 12.77 mgg−1μM−1, when MB concentration increased from 10 to
derstood by the comparative explanation of FT-IR spectrum of naked 60 mgL−1, at 27 °C (Table 3a).
Fe2O3–SnO2/BC and MB loaded Fe2O3–SnO2/BC. The large shifting in The Fe2O3–SnO2/BC has also shown superior partition coefficient
the position of the characteristic peaks of Fe2O3–SnO2/BC was observed values in comparison to the various previously reported adsorbents
in the FT-IR spectrum MB loaded Fe2O3–SnO2/BC (Fig. 7). The –OH (Table 3b). An analysis of the data in Table 3b reveals that super-
stretching vibrational frequency shifted from 3231 to 3222 cm−1 and absorbent hydrogel supported on modified polysaccharide, SH and
the absorption band at 1701 cm−1, appearing for –C]O, diminished copper nanoparticles prepared from cynomorium coccineum extract
which is the evidence for electrostatic as well as hydrogen bonding showed the superior maximum adsorption capacity (For SH,
interactions between the active sites of MB and –OH and –C]O groups 84.00 mgg−1 and for Cu NPs, 64.00 mgg−1) than tested Fe2O3–SnO2/
of Fe2O3–SnO2/BC, respectively (Siddiqui and Chaudhry, 2019). BC (58.82 mgg−1), however, their partition coefficients are lower than

Table 3a
Initial (Co) and equilibrium (Ce) concentration of MB solutions, and adsorption efficiencies, capacities, and partition coefficients of Methylene blue in contact with
Fe2O3–SnO2/BC.
Adsorbent Initial concentrations Equilibrium concentrations Maximum removal Adsorption capacity Partition coefficient
(mgL−1) (mgL−1) efficiency (%) (mgg−1) (mgg−1μM−1)

Fe2O3–SnO2/BC (Dose 2.0 gL-1, Time: 10 0.205 97.95 4.90 23.84


60 min, pH 7.0 and Temperature 27 °C) 20 0.548 97.26 9.72 17.76
30 0.900 97.00 14.55 16.17
40 1.355 96.61 19.32 14.26
50 1.870 96.26 24.06 12.88
60 2.260 96.23 28.87 12.78

10
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667

Paulino et al. (2006)

Hassan et al. (2017)

Sebeia et al. (2019)


Gupta et al. (2016)
Chaudhry (2019)
Siddiqui and
Summary of experimental data obtained for performance evaluation of adsorbents for removal of Methylene blue from water and their comparative Langmuir maximum Methylene blue removal capacities.

This study
References
Partition Coefficient, Kd
(mgg−1μM−1)

14.107

23.845
1.886

6.690

2.023
2.468
0.482
Maximum adsorption
(Langmuir) capacity

Fig. 7. FT-IR spectrum of MB loaded Fe2O3–SnO2/BC.

Fe2O3–SnO2/BC. Therefore, Fe2O3–SnO2/BC had the best performance


(mgg−1)

in terms of partition coefficient, i.e., 23.85 mgg−1μM−1. As mentioned


84.00

22.93
38.10

52.60
41.60
64.00

58.82

earlier the enhanced performance of present system might be due to


high functionality of Fe2O3–SnO2/BC which contributed towards ef-
fective chemical interaction of MB to Fe2O3–SnO2/BC as predicted
Co–Ce/m
(mgg−1)

above.
3.615

4.820
4.830

4.250
3.950
05.47

04.90

3.2.8. Regeneration and reusability


8.0

8.0
7.0

7.0

6.0

7.0
pH

As discussed in section 2.6, the MB loaded Fe2O3–SnO2/BC was


Temperature (°C)

regenerated by treating with 0.1M HCl solution for examining the


reusability of spent Fe2O3–SnO2/BC for further adsorption of MB. The
reusability of Fe2O3–SnO2/BC was monitored for numbers of con-
secutive adsorption-desorption cycles and obtained results revealed
20

25
27

30

22

27

that no significant reduction in the adsorption efficiency of


Fe2O3–SnO2/BC was observed till third cycles. However, after three
Adsorption dose, m

cycles the efficiency of Fe2O3–SnO2/BC decreased significantly, and


after seventh cycles of adsorption-desorption the efficiency of
Fe2O3–SnO2/BC reduce to approximately 65% (Fig. 9).
(gL−1)

1.0

4.0
2.0

2.0

2.5

2.0

3.2.9. Cost-estimation, features and implementation of Fe2O3–SnO2/BC


Before commercialization and implementation of Fe2O3–SnO2/BC,
Reaction time

the screening of health risk, life cycle, and estimation of cost is neces-
sary. The published literature showed that the organic-inorganic na-
(min)

nocomposites, being adsorptive material, can be employed for com-


150

40
60

24
15
30

90

mercial and home water treatment applications (Siddiqui and


Chaudhry, 2017a). They can be utilized as membrane for preventing
Final, Ce

the toxic contaminants, and kill the microbes, however the release of
1.917

0.720
0.342

2.100
1.600
11.33

0.205
MB Concentration

nanoparticles from composites can be dangerous on long term accu-


mulation (Siddiqui and Chaudhry, 2019). Therefore, prior to applica-
tion of nanocomposite in water treatment the laws and regulations
Initial, Co
(mgL−1)

established by various agencies for the production and application of


20.0

20.0
10.0

10.0

25.0

10.0

such material should be followed (Siddiqui and Chaudhry, 2017a). US-


EPA and EU-REACH are two most important governing bodies which
regulate the law and regulations for production, health effects, life and
Superabsorbent hydrogel supported on

application of materials in water treatment technology (Brame et al.,


Copper nanoparticles prepared from
cynomorium coccineum extract

2011; Gehrke et al., 2015).


Haloxylon recurvum plant stems

The design of the treatment plant should be cost effective so that it


modified polysaccharide

could reach to all sectors of society from commercial level to household.


The large scale plants need high cost for construction but once it con-
Potato leaves powder
Potato stem powder

structed it treat water at a nominal cost of 0.1–0.3 US$ per 1000 US gal
Fe2O3–SnO2/BC
Fe2O3–ZrO2/BC

(Siddiqui and Chaudhry, 2017a). In case of house hold plants, the cost
of construction is low but need around 100 US$ to treat 1000 US gal
Adsorbent
Table 3b

water (Brame et al., 2011; Siddiqui and Chaudhry, 2019). After as-
sessment of cost of plants, the cost of the material used in the household
plants should be affordable and comes under the regulations published

11
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667

Scheme 2. Proposed interaction between MB ions and Fe2O3–SnO2/BC.

implementing seven year plan (2014–2020) for promoting nano-


technology by spending 0.11 Trillion US$ (Gehrke et al., 2015; Siddiqui
and Chaudhry, 2019).
The nanocomposite material prepared in this study is affordable,
can be medicinally active with nontoxic nature due to bioactive Black
cumin seeds (Iqbal et al., 2017; Muhtasib et al., 2006). The estimated
cost per gram of Fe2O3–SnO2/BC came out 0.07 US$ which is lower
than the previously reported materials, iron-oxide nanoparticles, 1.20
US$, magnetite nanoparticles, 0.44 US$, titanium oxide nanoparticles,
0.18 US$, zero valent iron nanoparticles, 0.14 US$, and Black cumin
based iron-zirconium binary oxide, 0.10 US$ (Brame et al., 2011;
Siddiqui and Chaudhry, 2019). The chance of release of Fe2O3–SnO2
nanoparticles from Fe2O3–SnO2/BC is very low due to strong bonding of
Fe2O3–SnO2 nanoparticles with BC seeds and high generation rate
showed the long life of present adsorbent. Hence, Fe2O3–SnO2/BC has
excellent potential to meet the demands of water treatment, and can be
implemented affordably in household and commercial water treatment
Fig. 8. 3D-diagram for comparative study of partition coefficient, PC, and ad-
sorption capacity, Qe, over the change in concentration. plants.

3.3. Conclusion and future prospects

This study discussed the water treatment application of nanohybrid


composite, Fe2O3–SnO2/BC, composed of iron-tin binary oxide in-
corporated Black cumin seed powder. The simple co-precipitation
method was adopted for the preparation of the material for the appli-
cation in removing Methylene blue dye from aqueous solution. The
physiochemical properties of the prepared composite showed the nano-
cubic structure of Fe2O3–SnO2 having size in the range 95–185 nm,
trapped into the organic template of seed powder grains with high
functionality. The material, having zero point charge at pH 7.2, was
used in batch manner for Methylene blue adsorption from water. The
experiments were performed to optimize various process parameters
and the result revealed that 2.0 gL-1 dose was sufficient for 95% re-
moval of dye from solution having 10 mgL−1 concentration.
Fig. 9. Reusability of regenerated Fe2O3–SnO2/BC using 0.01M HCl solution. Thermodynamics data suggested spontaneous, feasible, and en-
dothermic nature of removal process. The adsorption data of the pro-
by various countries. Therefore, most of the countries are engaging cess fitted well to the Freundlich isotherm, whose kinetics followed the
their scientists to develop the materials for water treatment with rea- pseudo-second order and film diffusion model which clearly indicated
sonable and affordable cost. For this proposal, research and develop- the specific interaction between Methylene blue and appropriate
ment agencies of various countries are spending huge amount in the functional sites at the surface of Fe2O3–SnO2/BC. The Fourier-transform
production of affordable nanocomposite. European Union is infrared spectroscopy analysis gave evidence for hydrogen and elec-
trostatic interactions between the functional sites of Fe2O3–SnO2/BC

12
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667

and Methylene blue. The maximum Methylene blue adsorption capa- inaqueous solution. RSC Adv. 7, 336–343.
city, found to be in range 58.82–84.74 mgg−1 in the temperature range Dabrowski, A., 2001. Adsorption-from theory to practice. Adv. Colloid Interface Sci. 93,
135–224.
27–45 °C, was much higher than the other cited adsorbents. Therefore, Dong, R., Chen, D., Li, N., Xu, Q., Lu, J., 2019. Enhancement of organic pollutants bio-
this highly functionalized hybrid composite can be the advance option decontamination from aqueous solution using newly-designed Pseudomonas putida-
for water treatment. Thus selection of more pollutants for removal from GA/MIL-100(Fe) bio-nanocomposites. Environ. Res. 173, 237–245.
Dubinin, M.M., 1960. The potential theory of adsorption of gases and vapors for ad-
water using Fe2O3–SnO2/BC adsorbent can be more attractive to sorbents with energetically non-uniform surface. Chem. Rev. 60, 235–266.
achieve the better option. More laboratory and pilot scale investigations Elkady, M.F., El-Aassar, M.R., Hassan, H.S., 2016. Adsorption profile of basic dye onto
are needed to integrate this material to develop existing options of novel fabricated carboxylated functionalized Co-polymer nanofibers. Polymers 8,
177.
water treatment. For future research, the adsorption capacity of Ezechi, E.H., Mohamed Kutty, S.R.B., Malakahmad, A., Isa, M.H., 2015. Characterization
Fe2O3–SnO2/BC can be evaluated for multicomponent system i.e real and optimization of effluent dye removal using a new low cost adsorbent: equili-
water system. Real water has mixture of pollutants having various ions, brium, kinetics and thermodynamic study. Process Saf. Environ. Prot. 98, 16–32.
Gehrke, I., Geiser, A., Schulz, A.S., 2015. Innovations in nanotechnology for water
therefore, further studies on the influence of other competing ions on
treatment. Nanotechnol. Sci. Appl. 8, 1–17.
the adsorption capacity Fe2O3–SnO2/BC for MB is recommended. Ghorai, S., Sarkar, A., Raoufi, M., et al., 2014. Enhanced removal of methylene blue and
Furthermore, as the demand of multifunctional adsorbent increasing methyl violet dyes from aqueous solution using a nanocomposite of hydrolyzed
thus, antimicrobial activity of Fe2O3–SnO2/BC is also recommended. polyacrylamide grafted xanthan gum and incorporated nanosilica. ACS Appl. Mater.
Interfaces 6, 4766–4777.
Therefore, Fe2O3–SnO2/BC can be useful in all aspect for the develop- Giannakoudakis, D.A., Kyzas, G.Z., Avranas, A., Lazaridis, N.K., 2016. Multi-parametric
ment of advance water treatment technology. adsorption effects of the reactive dye removal with commercial activated carbons. J.
Mol. Liq. 213, 381–389.
Girod, M., Vogel, S., Szczerba, W., Thünemann, A.F., 2015. How temperature determines
Acknowledgment formation of maghemite nanoparticles. J. Magn. Magn. Mater. 380, 163–167.
Gu, C., Guan, W., Shim, J.J., Fang, Z., Huang, J., 2017. Size-controlled synthesis and
Authors are gratefully acknowledging the support provided by the electrochemical performance of porous Fe2O3/SnO2 nanocubes as an anode material
for lithium ion batteries. CrystEngComm 19, 708.
Department of Chemistry, Jamia Millia Islamia, and University Grant Guler, U.A., Ersan, M., Tuncel, E., Dügenci, F., 2016. Mono and simultaneous removal of
Commission, New Delhi, India, for carrying out the present research crystal violet and safranin dyes from aqueous solutions by HDTMA-modified
work. Spirulina sp. Process Saf. Environ. Prot. 99, 194–206.
Gupta, N., Kushwaha, A.K., Chattopadhyaya, M.C., 2016. Application of potato (Solanum
tuberosum) plant wastes for the removal of methylene blue and malachite green dye
Appendix A. Supplementary data from aqueous solution. Arab. J. Chem. 9, S707–S716.
Hassan, W., Farooq, U., Ahmad, M., Athar, M., Khan, M.A., 2017. Potential biosorbent,
Haloxylon recurvum plant stems, for the removal of methylene blue dye. Arab. J.
Supplementary data to this article can be found online at https://
Chem. 10, S1512–S1522.
doi.org/10.1016/j.envres.2019.108667. He, K., Zeng, G., Chen, A., Huang, Z., Chen, G., 2019. Graphene hybridized poly-
dopamine-kaolin composite as effective adsorbent for methylene blue removal.
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