Professional Documents
Culture Documents
Nigella Sativa Seed Based Nanohybrid Compositefe2 O3 SnO2 BC A Novel Material For Enhanced Adsorptive Removal of Methylene Blue From Waterenvironmental Research
Nigella Sativa Seed Based Nanohybrid Compositefe2 O3 SnO2 BC A Novel Material For Enhanced Adsorptive Removal of Methylene Blue From Waterenvironmental Research
Environmental Research
journal homepage: www.elsevier.com/locate/envres
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
2
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
3
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667
4
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667
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
Kλ
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.
5
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667
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
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
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)
10
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667
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
22.93
38.10
52.60
41.60
64.00
58.82
above.
3.615
4.820
4.830
4.250
3.950
05.47
04.90
8.0
7.0
7.0
6.0
7.0
pH
25
27
30
22
27
1.0
4.0
2.0
2.0
2.5
2.0
the screening of health risk, life cycle, and estimation of cost is neces-
sary. The published literature showed that the organic-inorganic na-
(min)
40
60
24
15
30
90
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
20.0
10.0
10.0
25.0
10.0
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
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.
References Compos. B Eng. 161, 141–149.
Hejtmancik, M.R., Ryan, M.J., Toft, J.D., Persing, R.L., 2002. Hematological effects in
F344 rats and B6C3F1 mice during the 13-week gavage toxicity study of Methylene
Ahmad, R., Haseeb, S., 2015. Black cumin seed (BCS): a non conventional adsorbent for blue trihydrate. Toxicol. Sci. 65, 126–134.
the removal of Cu (II) from aqueous solution. Desalin. Water Treat. 56, 2512–2521. Hosseinzadeh, H., Mohammadi, S., 2015. Quince seed mucilage magnetic nanocompo-
Al-Hamdi, A.M., Rinner, U., Sillanpää, M., 2017. Tin dioxide as a photocatalyst for water sites as novel bioadsorbents for efficient removal of cationic dyes from aqueous so-
treatment: a review. Process Saf. Environ. Prot. 107, 190–205. lutions. Carbohydr. Polym. 134, 213–221.
Arora, C., Soni, S., Sahu, S., Mittal, J., Bajpai, P.K., 2019. Iron based metal organic fra- Iqbal, M.J., Butt, M.S., Qayyum, M.M.N., Suleria, H.A.R., 2017. Anti-hypercholester-
mework for efficient removal of methylene blue dye from industrial waste. J. Mol. olemic and anti-hyperglycaemic effects of conventional and supercritical extracts of
Liq. 284, 343–352. black cumin (Nigella sativa). Asian Pac. J. Trop. Biomed. 7, 1014–1022 2017.
Badawy, M.I., Ali, M.E.M., Ghaly, M.Y., El-Missiry, M.A., 2015. Mesoporous Jiaqi, Z., Yimin, D., Danyang, L., Shengyun, W., Yi, Z., 2019. Synthesis of carboxyl-
simonkolleite–TiO2 nanostructured composite for simultaneous photocatalytic hy- functionalized magnetic nanoparticle for the removal of methylene blue. Colloid.
drogen production and dye decontamination. Process Saf. Environ. Prot. 94, 11–17. Surf. Physicochem. Eng. Asp. 572, 58–66.
Baltazar, A.R., Esparza, R., Rosas, G., Pérez, R., 2015. Effect of the surfactant on the Kataria, N., Garg, V.K., 2019. Application of EDTA modified Fe3O4/sawdust carbon na-
growth and oxidation of iron nanoparticles. J. Nanomater. 1–8 2015. nocomposites to ameliorate methylene blue and brilliant green dye laden water.
Basaleh, A.A., Al-Malack, M.H., Saleh, T.A., 2019. Methylene Blue removal using poly- Environ. Res. 172, 43–54.
amide-vermiculite nanocomposites: kinetics, equilibrium and thermodynamic study. Kim, H., Watthanaphanit, A., Saito, N., 2017. Simple solution plasma synthesis of hier-
J. Environ. Chem. Eng. 7, 103107. archical nanoporous mno2 for organic dye removal. ACS Sustain. Chem. Eng. 5,
Bentahar, S., Dbik, A., Khomri, M.E., Messaoudi, N.E., Lacherai, A., 2017. Adsorption of 5842–5851.
methylene blue, crystal violet and Congo red from binary and ternary systems with Li, D., Yang, Y., Li, C., Liu, Y., 2017. A mechanistic study on decontamination of Methyl
natural clay: kinetic, isotherm, and thermodynamic. J. Environ. Chem. Eng. 5, orange dyes from aqueous phase by mesoporous pulp waste and polyaniline. Environ.
5921–5932. Res. 154, 139–144.
Bharti, V., Vikrant, K., Goswami, M., Tiwari, H., Singh, R.S., 2019. Biodegradation of Li, X., Liu, Y., Li, S., et al., 2016. The sensing properties of single Y-doped SnO2 nanobelt
methylene blue dye in a batch and continuous mode using biochar as packing media. device to acetone. Nanoscale Res. Lett. 11, 470.
Environ. Res. 171, 356–364. Lozano, L.A., Iglesias, C.M., Faroldi, B.M., et al., 2018. Efficient solvothermal synthesis of
Bingol, D., Hercan, M., Elevli, S., Kılıc, E., 2012. Comparison of the results of response highly porous UiO-66 nanocrystals in dimethylformamide-free media. J. Mater. Sci.
surface methodology and artificial neural network for the biosorption of lead using 53, 1862–1873.
black cumin. Bioresour. Technol. 112, 111–115. Malakootian, M., Mansoorian, H.J., Hosseini, A., Khanjani, N., 2015. Evaluating the ef-
Boyd, G., Adamson, A., Myers, L., 1947. The exchange adsorption of ions from aqueous ficacy of alumina/carbon nanotube hybrid adsorbents in removing Azo Reactive Red
solutions by organic zeolites. II Kinetics. J. Am. Chem. Soc. 69, 2836–2844. 198 and Blue 19 dyes from aqueous solutions. Process Saf. Environ. Prot. 96,
Brame, J., Li, Q., Alvarez, P.J.J., 2011. Nanotechnology enabled water treatment and 125–137.
reuse: emerging opportunities and challenges for developing countries. Trends Food Mohamed, A., El-Sayed, R., Osman, T.A., Toprak, M.S., Uheida, A., 2016. Composite
Sci. Technol. 22, 618–624. nanofibers for highly efficient photocatalytic degradation of organic dyes from con-
Cao, Y.L., Pan, Z.H., Shi, Q.X., Yu, J.Y., 2018. Modification of chitin with high adsorption taminated water. Environ. Res. 145, 18–25.
capacity for methylene blue removal. Int. J. Biol. Macromol. 114, 392–399. Muhammad, S., Hussain, S.T., Waseem, M., et al., 2012. Surface charge properties of
Chaudhry, S.A., Ahmed, M., Siddiqui, S.I., Ahmed, S., 2016. Fe(III)-Sn(IV) mixed binary zirconium dioxide. Iran. J. Sci. Technol. 4, 481–486.
oxide-coated sand preparation and its use for the removal of As(III) and As(V) from Muhtasib, H.G., El-Najjar, N., Stock, R.S., 2006. The medicinal potential of black seed
water: application of isotherm, kinetic and thermodynamics. J. Mol. Liq. 224, (Nigella sativa) and its components. Adv. Phytomed. 2, 133–153.
431–441. Na, C.J., Yoo, M.J., Tsang, D.C.W., Kim, H.W., Kim, K.H., 2019. High-performance ma-
Chaudhry, S.A., Zaidi, Z., Siddiqui, S.I., 2017. Isotherm, kinetic and thermodynamics of terials for effective adsorptive removal of formaldehyde in air. J. Hazard Mater. 366,
arsenic adsorption onto iron-zirconium binary oxide-coated sand (IZOBCS): model- 452–465.
ling and process optimization. J. Mol. Liq. 229, 230–240. Nanda, B., Pradhan, A.C., Parida, K.M.A., 2016. Comparative study on adsorption and
Chauhan, M., Sharma, B., Kumar, R., Chaudhary, G.R., 2019. Green synthesis of CuO photocatalytic dye degradation under visible light irradiation by mesoporous MnO2
nanomaterials and their proficient use for organic waste removal and antimicrobial modified MCM-41 nanocomposite. Microporous Mesoporous Mater. 226, 229–242.
application. Environ. Res. 168, 85–95. Ong, C.B., Mohammad, A.W., Rohani, R., Ba-Abbad, M.M., Hairom, N.H.H., 2016. Solar
Chen, T., Xiong, Y., Qin, Y., et al., 2017. Facile synthesis of low-cost biomass-based g- photocatalytic degradation of hazardous Congo red using low-temperature synthesis
Fe2O3/C for efficient adsorption and catalytic degradation of methylene blue of zinc oxide nanoparticles. Process Saf. Environ. Prot. 104, 549–557.
13
S.I. Siddiqui, et al. Environmental Research 178 (2019) 108667
Paulino, A.T., Guilherme, M.R., Reis, A.V., et al., 2006. Removal of methylene blue dye methylene blue. Data Brief 20, 1044–1047.
from an aqueous media using superabsorbent hydrogel supported on modified Siddiqui, S.I., Ravi, R., Rathi, G., et al., 2018c. Decolorization of textile wastewater using
polysaccharide. J. Colloid Interface Sci. 301, 55–62. composite materials. In: Islam, S.U., Butola, B.S. (Eds.), Nanomaterials in the wet
Rahman, M.M., Glushenkov Ramireddy, T., Tao, T., Chen, Y., 2013. Enhanced lithium processing of textiles. John Wiley & Sons, Inc., pp. 187–218.
storage in Fe2O3-SnO2-C nanocomposite anode with a breathable structure. Siddiqui, S.I., Ravi, R., Chaudhry, S.A., 2019d. Removal of arsenic from water using
Nanoscale 5, 4910–4916. graphene oxide nano-hybrids. In: Naushad, M. (Ed.), A new generation material
Rahmi, Ishmaturrahmi, Mustafa, I., 2019. Methylene blue removal from water using graphene: applications in water technology. Springer, Cham, pp. 221–237.
H2SO4 crosslinked magnetic chitosan nanocomposite beads. Microchem. J. 144, Singh, G., Marimuthu, P., De Heluani, C.S., Catalan, C., 2005. Chemical constituents and
397–402. antimicrobial and antioxidant potentials of essential oil and acetone extract of Nigella
Sebeia, N., Jabli, M., Ghith, A., Saleh, T.A., 2019. Eco-friendly synthesis of Cynomorium sativa seeds. J. Sci. Food Agric. 85, 2297–2306.
Coccineum extract for controlled production of copper nanoparticles for sorption of Stan, M., Lung, I., Soran, M.L., Leostean, C., Porav, A.S., 2017. Removal of antibiotics
methylene blue dye. Arab. J. Chem. https://doi.org/10.1016/j.arabjc.2019.07.007. from aqueous solutions by green synthesized magnetite nanoparticles with selected
Siddiqui, S.I., Fatima, B., Tara, N., Rathi, G., Chaudhry, S.A., 2019a. Recent advances in agro-waste extracts. Process Saf. Environ. Prot. 107, 357–372.
remediation of synthetic dyes from wastewaters using sustainable and low-cost ad- Subramaniasiva, B., Nataraj, D., Mangalaraj, D., et al., 2009. Highly mesoporous α-Fe2O3
sorbents. In: Islam, S.U., Butola, B.S. (Eds.), The textile institute book series, The nanostructures: preparation, characterization and improved photocatalytic perfor-
impact and prospects of green chemistry for textile technology. Woodhead mance towards Rhodamine B (RhB). J. Phys. D Appl. Phys. 43, 015501.
Publishing, Elsevier, pp. 471–507. Szulejko, J.E., Kim, K.H., Parise, J., 2019. Seeking the most powerful and practical real-
Siddiqui, S.I., Chaudhry, S.A., 2017a. Iron oxide and its modified forms as an adsorbent world sorbents for gaseous benzene as a representative volatile organic compound
for arsenic removal: a comprehensive recent advancement. Process Saf. Environ. Prot. based on performance metrics. Separ. Purif. Technol. 212, 980–985.
111, 592–626. Tara, N., Siddiqui, S.I., Rathi, G., et al., 2019. Nano-engineered Adsorbent for the
Siddiqui, S.I., Chaudhry, S.A., 2017b. Arsenic: toxic effects and remediation. In: Islam, Removal of Dyes from Water: A Review. Curr. Anal. Chem. 15 In press.
S.U. (Ed.), Advanced materials for wastewater treatment. John Wiley & Sons, Inc., pp. Vikrant, K., Kim, K.H., 2019. Nanomaterials for the adsorptive treatment of Hg(II) ions
1–27. from water. Chem. Eng. J. 358, 264–282.
Siddiqui, S.I., Chaudhry, S.A., 2017c. Removal of arsenic from water through adsorption Vikrant, K., Kumar, V., Vellingiri, K., Kim, K.H., 2019a. Nanomaterials for the abatement
onto metal oxide-coated material. Mater. Res. Found. 15, 227–276. of cadmium (II) ions from water/wastewater. Nano Res. 12, 1489–1507.
Siddiqui, S.I., Chaudhry, S.A., 2017d. Arsenic removal from water using nanocomposites: Vikrant, K., Na, C.J., Younis, S.A., Kim, K.H., Kumar, S., 2019b. Evidence for superiority
A Review. Curr. Environ. Eng. 4, 81–102. of conventional adsorbents in the sorptive removal of gaseous benzene under real-
Siddiqui, S.I., Chaudhry, S.A., 2018a. Nigella sativa plant based nanocomposite- world conditions: test of activated carbon against novel metal-organic frameworks. J.
MnFe2O4/BC: a non-toxic, antibacterial material for water purification application. J. Clean. Prod. 235, 090–1102.
Clean. Prod. 200, 996–1008. Wang, H., Yao, Q., Wang, C., et al., 2016. A simple, one-step hydrothermal approach to
Siddiqui, S.I., Chaudhry, S.A., 2018b. A review on graphene oxide and its composites durable and robust superparamagnetic, superhydrophobic and electromagnetic wave-
preparation and their use for the removal of As3+ and As5+ from water under the absorbing wood. Sci. Rep. 6, 35549–35558.
effect of various parameters: application of isotherm, kinetic and thermodynamics. Wu, F.C., Tseng, R.L., Juang, R.S., 2009. Characteristics of Elovich equation used for the
Process Saf. Environ. Prot. 119, 138–163. analysis of adsorption kinetics in dye-chitosan systems. Chem. Eng. J. 150, 366–373.
Siddiqui, S.I., Chaudhry, S.A., 2019. Nanohybrid composite Fe2O3-ZrO2/BC for inhibiting Yang, J.M., Ying, R.J., Han, C.X., et al., 2018. Adsorptive removal of organic dyes from
the growth of bacteria and adsorptive removal of arsenic and dyes from water. J. aqueous solution by a Zr-based metal–organic framework: effects of Ce(III) doping.
Clean. Prod. 223, 849–868. Dalton Trans. 47, 3913–3920.
Siddiqui, S.I., Chaudhry, S.A., Islam, S.U., 2017. Green adsorbents from plant sources for Yari, S., Abbasizadeh, S., Mousavi, S.E., Moghaddam, M.S., Moghaddam, A.Z., 2015.
the removal of arsenic: an emerging wastewater treatment technology. In: Islam, S.U. Adsorption of Pb(II) and Cu(II) ions from aqueous solution by an electrospun CeO2
(Ed.), Plant-based Natural Products: Derivatives and Applications. John Wiley & nanofiber adsorbent functionalized with mercapto groups. Process Saf. Environ. Prot.
Sons, Inc., pp. 193–215. 94, 159–171.
Siddiqui, S.I., Manzoor, O., Mohsin, M., Chaudhry, S.A., 2019b. Nigella sativa seed based Zaidi, Z., Siddiqui, S.I., Fatima, B., Chaudhry, S.A., 2019. Synthesis of ZnO nanospheres
nanocomposite-MnO2/BC: an antibacterial material for photocatalytic degradation, for water treatment through adsorption and photocatalytic degradation: Modelling
and adsorptive removal of Methylene blue from water. Environ. Res. 171, 328–340. and process optimization. Mater. Res. Bull., 110584. https://doi.org/10.1016/j.
Siddiqui, S.I., Naushad, M., Chaudhry, S.A., 2019c. Promising prospects of nanomaterials materresbull.2019.110584. In press.
for arsenic water remediation: a comprehensive review. Process Saf. Environ. Prot. Zare, E.N., Motahari, A., Sillanpää, M., 2018. Nanoadsorbents based on conducting
126, 60–97. polymer nanocomposites with main focus on polyaniline and its derivatives for re-
Siddiqui, S.I., Rathi, G., Chaudhry, S.A., 2018a. Acid washed black cumin seed powder moval of heavy metal ions/dyes: a review. Environ. Res. 162, 173–195.
preparation for adsorption of methylene blue dye from aqueous solution: thermo- Zhu, J., Lu, Z., Ohnmar, O., et al., 2011. Synergetic approach to achieve enhanced lithium
dynamic, kinetic and isotherm studies. J. Mol. Liq. 264, 275–284. ion storage performance in ternary phased SnO2-Fe2O3/rGO composite nanos-
Siddiqui, S.I., Rathi, G., Chaudhry, S.A., 2018b. Qualitative analysis of acid washed black tructures. J. Mater. Chem. 21, 12770–12776.
cumin seeds for decolorization of water through removal of highly intense dye
14