Materials Today Communications 28 (2021) 102588

Contents lists available at ScienceDirect

Materials Today Communications

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

Iron oxide-loaded alginate-bentonite hydrogel beads as a green and

sustainable catalyst for 4-nitrophenol reduction
Subhadeep Biswas , Anjali Pal *
Civil Engineering Department, Indian Institute of Technology Kharagpur, West Bengal 721302, India

A R T I C L E I N F O A B S T R A C T

Keywords: The development of sustainable green catalysts is always a challenging task. Besides this, the catalyst should be
Iron oxide-loaded alginate-bentonite hydrogel recyclable and hence cost-effective. In the present work, alginate hydrogel beads were used as a support of iron
beads oxide to form iron oxide-loaded alginate beads (Io-alg). Alginate is a biopolymer, cheap, and nontoxic. Iron is
Sustainable green catalyst
abundant in nature and a non-toxic element. To improve the mechanical stability of the beads, bentonite was
4-nitrophenol reduction
4-aminophenol
used to form iron oxide-loaded alginate-bentonite composite beads (Io-alg-ben). Bentonite is an inorganic ma­
Zero-order reaction terial, easily available. Both Io-alg and Io-alg-ben beads in hydrogel conditions were deployed as the supported
catalyst for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in borohydride environment. It is
interesting to observe that hydrogel beads showed excellent catalytic activity toward 4-NP reduction. The zero-
valent iron (ZVI) produced in-situ during the 4-NP reduction under NaBH4 medium was the active catalyst for 4-
NP reduction. The reduction was examined using various catalyst doses and various initial concentrations of 4-
NP, and in all cases the reaction followed zero-order kinetics. The catalyst could be reused up to 5 cycles without
any loss of efficiency. The turnover number (TON) and turnover frequency (TOF) of the catalyst were found as
4.3 × 1019 molecules/g and 3.09 × 1017 molecules/g/s for Io-alg-ben hydrogel beads. The performance is
comparable with other reported catalysts. The effect of reaction temperature was also investigated to find out the
activation energy. Thus, a sustainable iron oxide-loaded alginate-bentonite supported catalyst has been devel­
oped for the efficient reduction of 4-NP to 4-AP. The novelty of the present work is that here the iron-oxide
loaded alginate-bentonite hydrogel beads are stable, economical, nontoxic, and reusable for many cycles.

1. Introduction
Among various recalcitrant organic products released in the indus­
trial wastewater 4-nitrophenol (4-NP) is one of the predominant ones.
Industries like synthetic dyes, pesticides, herbicides, pharmaceuticals,
refineries, coal processing industries release 4-NP as one of their waste
products [1]. The USEPA has listed 4-NP as a criteria pollutant. Phenolic
compounds are usually highly soluble in water [2]. Besides this some of
them are potential carcinogens [3] and mutagens [4]. They have the
potential of damaging DNA or inhibiting the synthesis of DNA which in
turn affects blood, liver, and central nervous system adversely. On the
other hand, 4-aminophenol (4-AP), one of the products formed by the
reduction of 4-NP, is a valuable compound and has wide applications in
the drug industry [1]. It is also used as an anticorrosive reagent for
paints, and as a photographic developer. It also serves as a wood stain
and dyeing agent for fur and feathers in the dye industry. Moreover, the
natural degradation of 4-NP is a time-consuming process and there is a
chance that it gets accumulated in the soil surface. Hence conversion of
4-NP to 4-AP can be considered as an effective waste management
procedure. Due to this reason, 4-NP to 4-AP conversion by using various
newly developed catalysts has become one of the common research
topics for the last few decades.
The performance of catalytic reduction of 4-NP by embedded gold
and silver nanoparticles has been reported by various researchers
[5–18]. There are several reports where Ni [19–21], Cu [22], Co [23],
and Pd [24] nanoparticles were used for such purpose. Composite ma­
terials [25] are also used as catalyst to reduce 4-NP in borohydride
medium. One of the major difficulties faced while attempts have been
made for catalytic reduction with metal nanoparticles (MNPs) is the
aggregation of the MNPs due to van der Waal’s interaction and loss of
surface area of the catalyst leading to significant reduction in catalytic
efficiency [26]. Polymers are often used to provide support and stability
to the heterogeneous catalysts. Although various types of supports are
available from the point of sustainability and green chemistry,

* Corresponding author.
E-mail address: anjalipal@civil.iitkgp.ac.in (A. Pal).

https://doi.org/10.1016/j.mtcomm.2021.102588
Received 22 February 2021; Received in revised form 12 June 2021; Accepted 21 June 2021
Available online 25 June 2021
2352-4928/© 2021 Elsevier Ltd. All rights reserved.
S. Biswas and A. Pal
biopolymers have become an attractive proposition. Gao et al. [27,28]
used lignin-supported MNPs for 4-NP degradation. Tomke and Rathod
[29] used chitosan support while Khan et al. [26] utilized
chitosan-coated polyurethane sponge support based MNPs for 4-NP
reduction. The supported catalytic systems are more attractive than
the homogeneous systems in terms of recovery of the catalyst. Some
plant extracts have also been reported as an efficient stabilizer for MNPs.
The reduction efficiency of zerovalent iron (ZVI) is well understood
and has been applied by several research groups for environmental
remediation purposes. ZVI has been used by many researchers for the
remediation of wastewater containing refractory wastes such as nitro­
benzene containing waste, olive mill waste, etc. The reduction of 4-NP in
the presence of Fe(0) and borohydride is chemically feasible. However,
the number of studies of 4-NP reduction by ZVI as a catalyst is very less
in comparison to that catalysed by Au and Ag. Iron is the fourth most
abundant metal available on the earth’s crust and more importantly, ZVI
is non-toxic and inexpensive. Although 4-NP reduction by zero valent
iron catalyst is feasible but various restrictions such as maintenance of
inert nitrogen atmosphere (as it is vulnerable to oxidation), quick uti­
lisation of zero valent iron because of the problem of aggregation, and
the presence of impurity in the zero valent iron available in the market
have been reported in literature [30–33]. Some researchers also used bio
extracts of eucalyptus leaf [34], Euphorbia neriifolia L. leaf [35], Melissa
officinalis L leaf [36] for stabilising catalyst for 4-NP reduction purpose.
Thus it is well understood, that an in-situ preparation of ZVI can be a
better alternative than preparing it and storing it for a longer time until
further use. Moreover, it is easier to recover the prepared ZVI when it is
placed on a suitable support. In the present work, first hydrogel polymer
(e.g. alginate and alginate-bentonite composite) beads impregnated
with iron oxide was synthesised. This is our precursor catalyst. The
material is very stable and can be stored for months together under
ambient condition. In the second step, during the 4-NP reduction in the
presence of NaBH4, the supported iron oxide was simultaneously
reduced to ZVI which served as the active catalyst. No extra stabilizer
was used to preserve ZVI and no inert atmosphere was required to
prevent the oxidation of ZVI. Alginate, which is an environment-friendly
biopolymer and often used as a drug carrier for controlled release of
drugs, was the support cum stabilizer of ZVI. The chemical structure of
alginate bears COOH and OH groups. The utilization of alginate hy­
drosol and as hydrogel beads as a stabilizer and a template for MNP
synthesis has been reported earlier [37,38]. Bentonite was mixed with
the alginate to provide better mechanical strength to the hydrogel beads
and to ensure better stability to ZVI.
The present study focuses on the comparative analysis of the cata­
lytic activity of iron oxide-loaded alginate (Io-alg) and iron oxide-loaded
alginate-bentonite (Io-alg-ben) beads for 4-NP reduction. It was high­
lighted by Ibanez and Umetsu [39] that, the dried beads are more
consistent in terms of weight and they are more convenient to handle for
a practical purpose. However, in our case dried beads did not serve as a
catalyst for 4-NP reduction. The unique structural features of hydrogel
not only causes the metal NPs to disperse well but also provides an
excellent environment for different reactions, especially, in aqueous
phase catalysis. The typical chemical structure of hydrogel is responsible
for the adsorption of metal ions onto the gel, and also it helps in con­
trolling the nanoparticle size. Moreover, due to the polymeric gel
structure, it prevents the agglomeration of the nanoparticles during the
in-situ preparation. Further, its structure can influence the catalytic
reduction of 4-NP. However, till date studies on the utilisation of
hydrogel beads as catalyst support for 4-NP reduction are less in num­
ber. In this work, various parameters such as initial concentration of
4-NP, dose of catalyst, effects of catalyst loading on the alginate and
bentonite-modified alginate hydrogel beads have been studied to find
out the optimum condition. The catalyst may have potential for real field
application because of its high catalytic activity, reproducibility and
reusability. Besides this, the in-situ generation of the ZVI catalyst is often
desirable in terms of 4-NP reduction performance, as in many cases
2
Materials Today Communications 28 (2021) 102588
growing microelectrode (GME) is more effective than the full-grown
electrode (FGME) [8].
2. Materials and methods
2.1. Reagents and apparatus
Alginate powder, FeCl2, NaBH4 were purchased from Loba Chemie.
Bentonite powder was procured from Wako, Japan. 4-Nitrophenol (4-
NP), concentrated HCl (37%) was bought from Merck. A stock solution
of 4-NP (1 ×10− 2 M) was prepared in Millipore water. All the chemicals
were of high purity and they were used without further purification.
The morphological features of alginate (designated as Alg) alginate-
bentonite beads (designated as Alg-ben), iron oxide-loaded alginate
(designated as Io-alg) and iron oxide-loaded alginate-bentonite (desig­
nated as Io-alg-ben) beads (after oven drying) were studied via scanning
electron microscopy (SEM) on a JEOL JSM5800 microscope. To identify
the functional groups, present in alginate, bentonite, and iron oxide-
loaded beads, Fourier transform Infrared (FTIR) spectra were recorded
in Perkin Elmer, Thermo Nicolet (USA) spectrophotometer. Absorbance
values were measured in a UV–visible spectrophotometer (Agilent)
using a quartz cuvette. The pH meter was procured from GENEI, India.
The loading of iron oxide on the beads was determined using AAS
(Varian, India).
2.2. Synthesis of different hydrogel beads
In the present work four different kinds of hydrogel beads (and their
derived forms) viz., alginate (Alg), alginate-bentonite (Alg-ben), iron
oxide-loaded alginate (Io-alg) and iron oxide-loaded alginate-bentonite
(Io-alg-ben) were prepared, characterized and finally their catalytic
activity towards 4-NP reduction was examined. The material prepara­
tion is shown schematically in the flowchart (Fig. S1) and their prepa­
ration procedure is described in detail as follows:
The alginate hydrogel beads were prepared following the procedure
described earlier [10]. Alginate solution was prepared by dissolving 0.1
g of alginate powder in 5 mL of Millipore water. In the case of
alginate-bentonite composite preparation, the only difference was that
during the preparation of alginate-bentonite beads 0.1 g of bentonite
was also mixed with 0.1 g of alginate powder in 5 mL Millipore water.
The resulting solution having alginate concentration of 2% w/v was
continuously stirred in a magnetic stirrer at room temperature (30 ± 2
⁰C) for 1 h till it turned in to a homogeneous solution. A solution con­
taining CaCl2 (4% w/v) was already prepared by dissolving 2 g of CaCl2
in 50 mL of Millipore water. The alginate or alginate-bentonite solution
was then added drop by drop separately to the solution using 1 mL
micropipette. Spherical uniform beads started forming instantaneously
through cross-linking. The newly formed beads were kept immersed in
the same CaCl2 solution for 24 h and then thoroughly washed with
Millipore water to remove the chloride ion. The alginate beads were
designated as Alg beads and the alginate-bentonite composite beads
were named as Alg-ben beads (Fig. S1).
During the preparation of iron oxide-loaded hydrogel beads, first the
alginate or alginate-bentonite solution was prepared following the
already described procedure. A solution containing CaCl2 and FeCl2 (10
g/L) was already prepared by dissolving 2 g of CaCl2 and 0.5 g of FeCl2 in
50 mL Millipore water. The alginate/ alginate-bentonite solution was
then added drop-wise to the solution using a 1-mL micropipette.
Spherical uniform beads started forming instantaneously through cross-
linking. The newly formed beads were allowed to stay in CaCl2 solution
and then thoroughly washed with Millipore water to remove the chlo­
ride ions and loosely bound metal ions present on the beads. The beads
so formed were designated as Io-alg (for iron-oxide loaded alginate) and
Io-alg-ben (for iron-oxide loaded alginate-bentonite) hydrogel beads
(Fig. S1).
S. Biswas and A. Pal Materials Today Communications 28 (2021) 102588

Fig. 1. Schematic of 4-NP reduction in presence of Io-alg-ben hydrogel beads as catalyst.

2.3. Analytical methods
2.3.1. Determination of iron loading on the beads
It was very important to find out the loading of iron on the beads. To
find out the iron loading on the Io-alg-ben beads, a measured number of
beads were dipped in a definite volume of concentrated HCl solution
taken in each of two 50-mL glass beakers covered with a petri dish. The
solution was kept at rest with occasional handshaking for 30 min. After
some time, the acid solution turned to yellow due to the leaching of iron
(Fig. S2). In many industrial processes when metal recovery from a
complex matrix is required, the leaching procedure using mineral acids
is often adopted [40]. For preparing Io-alg-ben beads, two initial con­
centrations of FeCl2 (10 g/L and 40 g/L) were tried out. Both types of
beads were subjected to the same leaching procedure followed by 10 and
100 times successive dilutions. Finally, the diluted leachates were tested
for total iron concentration using AAS, and the loadings were found to
be 82 mg/g and 102 mg/g of dry beads for the two initial FeCl2 con­
centrations e.g. 10 g/L and 40 g/L, respectively.
2.3.2. Determination of 4-NP concentration
Initially, a calibration curve was plotted by adding a suitable amount
of 4-NP in the borohydride solution without any catalyst. 4-NP has a
typical absorption peak at 317 nm in neutral media. Upon the addition
of borohydride, the solution became alkaline and showed a strong ab­
sorption peak at 400 nm due to the formation of nitrophenolate ion. The
calibration curve drawn at 400-nm peak is shown in Fig. S3. The

Fig. 2. Photographic images of Io-alg (a) and Io-alg-ben (b) hydrogel beads.

3
S. Biswas and A. Pal
equation for the calibration curve is: Absorbance = 0.025 × Conc. (µM)
+ 0.396 (R2 = 0.993). The remaining concentrations of 4-nitrophenolate
ion present at different times of 4-NP reduction were calculated using
this calibration curve.
2.4. Reduction of 4-NP
The reduction of 4-NP by NaBH4 in presence of Io-alg hydrogel beads
and Io-alg-ben hydrogel beads were carried out in a standard stoppered
quartz cuvette under ambient condition. During the 4-NP reduction by
NaBH4 the supported iron oxide were instantaneously reduced to zero
valent iron (ZVI) which was the actual catalyst. The absorption spectra
of the reaction mixture were monitored to examine the reduction of 4-
nitrophenolate ion. In a typical procedure, 2.5 mL of NaBH4 solution
(0.1 M) was mixed with an appropriate volume of stock 4-NP (1 × 10− 2
M). Subsequently, the solution turned to bright yellow due to the for­
mation of 4-nitrophenolate ion. Next, a suitable number of hydrogel
beads loaded with iron oxide was added, and the solution was quickly
subjected to UV–vis spectral measurements. Afterward, the absorbance
at 400 nm was measured at certain time intervals to obtain the succes­
sive changes in the concentration of the 4-nitrophenolate ion. The
schematic of the reaction is shown in Fig. 1. It is to be noted that in all
experiments hydrogel beads were used.
3. Results and discussion
3.1. Physical characteristics of the beads
The photographic images of the Io-alg and Io-alg-ben composite
hydrogel beads have been shown in Fig. 2(a) and (b), respectively. The
beads were nearly uniform and spherical in shape having the average
diameter in the range of 3.3–3.5 mm. In the texture there was a notable
difference between the normal Alg-ben and Io-alg-ben hydrogel beads.
Moreover, the beads with bentonite were a bit stronger than the beads
without bentonite and it can be felt simply by hand pressing. After iron
adsorption, a typical brownish color appears in the beads. The moisture
content and dry weight of both Io-alg and Io-alg-ben beads have been
calculated as an average of 30 beads. The results are compiled in
Table S1.
Besides the physico-chemical characterization presented in this
section, other common characterization procedures such as XRD, XPS,
BET, TEM analysis have not been carried out for the as-prepared ma­
terials as because in our case the catalytic reduction of 4-NP was con­
ducted with hydrogel beads only. It is important to be mentioned here
that, although the iron was added to the hydrogel beads in Fe+2 form but
it might have partly or fully converted to + 3 state in presence of air, as
iron has a strong tendency to get oxidised. However, knowing this
oxidation state is insignificant as in presence of NaBH4 (a strong
reducing agent) it would have been fully converted to ZVI, and it is the
actual catalyst. Moreover, verifying the oxidation state of iron within the
hydrogel bead matrix by means of XPS analysis is not feasible physically.
Moreover, the XPS analysis of the dried beads would not reflect the
actual oxidation state of iron present in the catalyst because during the
drying procedure the oxidation state of iron may change readily.
Moreover, to conduct XRD, TEM and BET characterization it is
necessary to use only dry beads, which is not our actual catalyst. Thus,
these tests may not truly depict the feature of the hydrogel beads, and
hence may not give proper insight in to the catalytic reduction process.
However, in order to know the morphology of the surface and to get an
idea about the functional groups present in the composite materials, the
SEM and FTIR analyses of the dried beads were carried out. The SEM
images of Alg, Alg-ben, Io-Alg and Io-alg-ben are shown in Fig. S4 and
the morphology of the materials are described in the Supplementary
information. The results of FTIR analysis are described in the Supple­
mentary information (Table S2) and the spectra of Alg, Alg-ben, FeCl2
and Io-alg-ben are shown in Fig. S5.
4
Materials Today Communications 28 (2021) 102588
3.2. Specific surface area of the hydrogel beads
As the catalyst used in our work are hydrogel beads having > 95%
moisture content, so specific surface area of dry beads determined by
means of BET analysis would not depict the true catalyst surface char­
acteristics. Hence the specific surface area of the hydrogel beads has
been estimated after modification of methylene blue (MB) adsorption
method as described by previously published article [41]. 5-mL aliquots
of MB solution having concentration 500 mg/L were taken in two 30-mL
glass vials and 10 hydrogel beads each of Io-alg and Io-alg-ben were
inserted in to the solutions separately. Same experiment was performed
with MB solution having concentration 2000 mg/L also. After 7 days
when the equilibrium was attained, the absorbance values of all the dye
solutions were measured after proper dilution. The specific surface area
was calculated by the following formula:
mMB 1
SSA = Av AMB
319.87 ms
Here, SSA refers to the specific surface area of the hydrogel beads,
mMB refers to the mass of methylene adsorbed (g), Av indicates Avogadro
number, AMB indicates specific surface area of methylene blue molecule
(130 × 10− 20 m2) and ms refers to the mass of the adsorbent (g).
The average specific surface area for Io-alg-ben beads were obtained
as ~178 m2/g and that for Io-alg beads as ~244 m2/g. It is quite high in
comparison to the specific surface area obtained for dried beads by BET
method reported in other studies [42]. However, due to carbonisation,
in some cases high specific area has also been reported [43].
3.3. Catalytic reduction of 4-NP
The absorption peak of 4-NP shifts from 317 nm to 400 nm upon
addition of borohydride. This is due to the conversion of the phenolic
OH group to phenolate ion in alkaline conditions produced by NaBH4.
The reduction of the nitro group of 4-NP to produce 4-AP upon addition
of catalyst (Io-alg-ben hydrogel beads) starts with the concurrent gen­
eration of a new peak at 293 nm. The initial yellow color of the 4-nitro­
phenolate vanishes gradually with time. The color change can be
observed in the naked eye also. The time-dependent absorption spectra
are shown in Fig. S6. The formation of a single isosbestic point at 316 nm
indicates that, the 4-AP is the single product formed during the reaction
[10].
It was very much important to justify the loading of iron oxide on the
alginate (Alg) and alginate-bentonite (Alg-ben) hydrogel beads as ZVI is
the catalyst for 4-NP reduction. The 4-NP reduction was also conducted
in the presence of alginate hydrogel beads without any loaded iron oxide
to examine its catalytic property. The catalytic behavior of Alg and Io-
alg-ben towards the 4-NP reduction has been shown in Fig. S7. Algi­
nate has been well known for its reducing and biosorption properties.
But in the case of Alg beads, even after 2.5 h, the 4-NP reduction did not
occur. Moreover, no new peak at 293 nm appeared during this 2.5 h
time. The slight decrease in the absorbance value at 400 nm on Alg
beads (as observed in Fig. S7) may be due to the adsorption of 4-nitro­
phenolate ion on the bead surface. This is very similar to the findings
of our previous work on 4-NP reduction by Ag-loaded dried calcium
alginate beads [10]. It was interesting to observe that, the reduction of
4-NP by borohydride did not start immediately after the addition of
Io-alg-ben hydrogel beads. An induction time was required for the
in-situ formation of ZVI and for the proper development of a catalytic
environment for 4-NP reduction. This phenomenon was realized in
previous studies. Wunder et al. [44] stated that this induction time was
needed for the surface reconstruction of the nanoparticles at the surface.
The reason behind this lag may also be due to the dissolved oxygen
present in water. The dissolved oxygen reacts first with borohydride,
then the nitrophenol reduction takes place [10]. The other possible
reason is that, because the catalyst is supported on the hydrogel beads so
nitrophenolate ion may take some time to come to the close contact of
S. Biswas and A. Pal
Fig. 3. Kinetics of 4-NP reduction (at two different concentrations: 40 µM and
60 µM) in presence of Io-alg-ben (dose 0.84 g/L) and NaBH4 (0.1 M).
ZVI. However, in some cases (e.g. in the presence of Ag-loaded alginate
dry beads) no induction time was required to start the reaction [10].
3.3.1. Formation of ZVI as growing microelectrode (GME) or full-grown
microelectrode (FGME) and reduction of 4-NP
It is assumed that the 4-NP reduction is via two steps: in the first step
the formation of ZVI growing microelectrode (GME) or full-grown
microelectrode (FGME) from higher oxidation state of iron takes place
in presence of NaBH4, and in the second step it successively accelerates
the transfer of an electron from BH-4 to 4-NP. The use of iron oxide-
loaded Alg-ben is beneficial compared to ZVI-loaded Alg-ben in terms
of stability and sustainability. It is well known that the reaction is
thermodynamically favourable with E0 = − 0.76 V (vs. NHE) for 4-NP/4-
AP and − 1.33 V (vs. NHE) for H3BO3/BH-4, but it is kinetically very slow
in absence of any catalyst. Even after two days, there was no significant
change in the absorption value at 400-nm peak if no catalyst was added.
In the presence of ZVI catalyst borohydride ions transfer hydride ions to
the surface of the hydrogel beads and it causes the reduction of 4-NP.
According to the report of Gu et al. [45] the reduction of NP again oc­
curs in two steps. The first step involves the formation of 4-hydroxyami­
nophenol which is a stable product. In the second step,
4-hydroxyaminophenol gets reduced to 4-AP. In the present case, the
reduction of 4-NP in borohydride medium and in the presence of ZVI
nanoparticles as the catalyst has been found to follow zero-order kinetics
which is very similar to one of the previous reports [10]. The reaction
mechanism can be described either by the Eley-Reidel (E-R) mechanism
or the Langmuir-Hinselwood (L-H) mechanism. Nakatsuji et al. [46]
reported the 4-NP reduction in the presence of ZVI to follow the modi­
fied L-H model. The exact mechanism, however, can be predicted from
detail kinetic study and product identification.
Table 1
Performance comparison of 4-NP reduction in presence of iron-based catalysts.
Catalyst description 4-NP (M)
Nano zero-valent iron 0.1 × 10−
− 4
Zero valent iron immobilized on the bentonite clay surface using Eucalyptus leaf 2 × 10
extract as stabiliser and reducing agent
Chitosan based nano zero valent iron 2.06 × 10
Zerovalent iron synthesised and stabilized by extracts of Azadirachta indica 2.5 × 10−
Iron oxide-alginate-bentonite hydrogel beads 6 × 10− 5
5
Materials Today Communications 28 (2021) 102588
3.3.2. Variation of catalyst dose and initial concentration of 4-NP
4-NP degradation using Io-alg and Io-alg-ben was conducted at two
different initial concentrations of 4-NP viz., 40 and 60 µM and with two
different catalyst doses (3 and 5 hydrogel beads) of each type. The
catalyst doses calculated in terms of dry beads and in terms of loaded
iron are compiled and the corresponding results are shown in Table S3.
In all cases, the reduction followed zero-order kinetics. As the 4-NP
reduction occurred in the presence of an excess (with respect to the 4-
NP concentration) of borohydride, so some researchers preferred to
describe the reaction to follow pseudo-first order rate with respect to 4-
NP concentration [15]. But in our case, the reaction is well described by
the zero-order reaction. Thus, the reduction can be defined as a true
surface catalysed reaction. This result is similar to one of the previous
studies of 4-NP reduction by Ag-loaded calcium alginate beads [10].
However, in most of the studies reported earlier, the first order fit has
been reported for such type of 4-NP reduction [8,19].
Fig. 3 shows the comparative zero-order kinetic plot (concentration
vs. time) of 4-NP reduction at two different initial 4-NP concentrations
(40 and 60 µM) using Io-alg-ben catalyst at a dose of 0.84 g/L. It is
interesting to note that the reduction rate constant increases with an
increase of initial 4-NP concentration (Table S3). Since the reaction
follows zero-order rate so the rate constant should ideally be indepen­
dent of the initial concentration. However, in this case the rate constant
slightly varies with variation of initial 4-NP concentration. Similar re­
sults have also been reported in the case of degradation of 2,4-dichloro­
phenoxyacetic acid (2,4-D) by UV light following zero-order rate [47].
In the present case, the 4-NP molecules first diffuse through the bulk
solution and then get adsorbed onto the surface of the hydrogel beads
and finally are reduced. Now if the initial concentration is increased, the
diffusion will be faster which will affect the final rate of reduction.
Table S3 shows the comparative rate constant values for 4-NP reduction
at two different concentrations of 4-NP using two different doses of the
catalysts Io-alg and Io-alg-ben. It was observed that for both the catalysts
when catalyst dose is increased at a fixed 4-NP concentration, the rate
constants decrease. This is not common. The exact reason can be found
out in more investigations.
Many naturally occurring biopolymer beads are found to be suitable
adsorbent and can be used for environmental remediation purposes.
This is because of the presence of several functional groups. For example
the –COOH groups present in alginate have the ability to complex with
metal ions. In addition to this, the metal ions can be attached to alginate
matrix by ionic attraction. However, gel beads are often reported to be
suffering from adequate mechanical strength. To gain mechanical sta­
bility they are often mixed with different clay materials such as
bentonite, zeolite etc. Besides that, these clay materials have a large
number of binding sites for metal ions and have a large surface area
[48]. Thus, they serve as excellent support material. It is also revealed
from the previous research works that bentonite possesses a unique
layered structure which is very much congenial for loading, fixation, and
padding of ZVI [49]. The experimental results of Diao et al. [50] showed
that bentonite can serve as a perfect template for preventing aggregation
and it can help in well dispersion of nano ZVI. If the reaction rate
Dose NaBH4 conc. Order Rate constant Reference
(mg/L) (M)
3 2 1 1
3.5 5 × 10− Pseudo- 3.1 × 10− min− [30]
first
− 1 − 1
10 0.2 Pseudo- 1.4 × 10 min [34]
first
− 4 − 2 − 3 − 1
1000 2 × 10 Pseudo- 2.45 × 10 s [51]
first
4 1
30 µL 2.5 × 10− [52]
840 1 × 10− 1 Zero 22.58 × 10− 6
This work
M min− 1
S. Biswas and A. Pal Materials Today Communications 28 (2021) 102588

Fig. S3) the remaining concentration of 4-NP in the solution at this point
was calculated and it was found to be ~5 µM. So approximately 90% of
the reduction is complete at this point. The whole plot of absorbance vs.
time is shown in Fig. 4.

3.3.4. Role of support materials and bio-extracts in stabilizing metal

nanoparticles
Due to the possession of phenols, flavonoids, etc., various bio ex­
tracts have been found to stabilize metallic nanoparticles. For example,
Bordbar et al. [36] synthesized CuO/ZnO nanocomposites by using
Melissa officianalis extract. Sravanthi et al. [53] used Calotropis gigantia
flower extract for ZVI synthesis. Euphorbia wallichi leaf extract was also
explored by Atarod et al. [54] for the preparation of Fe3O4 nano­
composite. The biomolecule alginate used in our work during ZVI
preparation has the functional groups like –COOH, -OH, etc., which can
impart chemical stability to ZVI.
Besides this, the support materials play a very important role in
heterogeneous catalysis. Robust support is necessary for the easy re­
covery of the catalyst after the reaction. There are also some evidence
from the literature that showed the dispersion of ZVI in material sup­
port. Alginate has been reported in some studies as a perfect holder for a
metal catalyst. In earlier reports alginate has been shown to be an
excellent template for Ag and Au nanoparticle catalysts for the reduction
Fig. 4. Plot of absorbance vs. time throughout the entire period of 4-NP
of 4-NP to 4-AP [10]. Xia et al. [55] used it for palladium support for
reduction in presence of Io-alg-ben hydrogel beads as catalyst. [4-NP]
= 60 µM, dose = 0.84 g/L.
4-NP reduction. But inadequate mechanical strength is often an issue for
the hydrogel beads. Moreover, it has also been reported in one of the
recent studies that bentonite has good compatibility with alginate
constant for two types of beads (i.e Io-alg and Io-alg-ben) is compared,
polymer due to hydrogen bonding and electrostatic attraction between
then it is clear (from Table S3) that Io-alg-ben hydrogel beads have
them [56]. Montmorillonite which is a major constituent of bentonite is
higher catalytic activity compared to that of Io-alg hydrogel beads. So,
well known for its lamellar structure and exfoliation properties in
apart from the high strength gained due to the incorporation of
aqueous environment owing to the strong hydration of the sorbed cat­
bentonite, the inclusion of bentonite offers a better reaction environ­
ions in the interlayer. It has also been reported to impart higher me­
ment for 4-NP reduction. The performance of various iron-based cata­
chanical and thermal strength to various hydrogel matrices. So, to
lysts [30,34,51,52] used by different researchers for the reduction of
synthesize a more stable catalyst, bentonite is used along with alginate
4-NP has been summarised in Table 1.
to form the support.
3.3.3. Kinetic study on 4-NP reduction
3.3.5. Effect of iron loading on 4-NP reduction efficiency
To have an insight into the kinetics of the reduction reaction, the
As the reaction was catalysed by ZVI, so it was important to see the
absorbance value at 400 nm (due to 4-nitropheenolate ion) has been
effect of loaded iron concentration on hydrogel beads. To vary the
plotted against time (min). From the graphical presentation shown in
loading of iron on Io-alg-ben beads two initial concentrations of FeCl2
Fig. 3, using the catalyst dose 0.84 g/L and 4-NP concentration 60 µM, it
(10 g/L and 40 g/L) were used during bead preparation. The beads
is clear that at the initial phase, the reaction does not occur and some
formed with higher iron content are darker in colour. It is found that
induction time (~6 min) is required for the development of fully-grown
with the catalyst having higher iron content the rate of 4-NP reduction is
microelectrode (FGME) of ZVI in Io-alg-ben hydrogel beads. After this
a bit faster. But the black colour formed over the surface of the hydrogel
period, the beads turn black, and from this time the absorbance value
beads during 4-NP reduction is found to be more intense in case of lower
linearly decreases with time and ultimately comes to a constant value in
iron contained beads. In case of higher iron contained beads, the black
2 min. Hence the reaction can be described as a zero-order reaction
colour formed due to ZVI over the hydrogel bead surface is slightly
which is an indication of surface catalyzed reaction. Such type of zero-
inhomogeneous. In addition to this, it is noticed that after the reaction,
order reaction has been noticed for the first time for a 4-NP reduction
the beads with iron in lower quantity are much more stable compared to
in the presence of Ag and Au nanoparticles in calcium alginate bead
the beads with higher amount of iron. The beads with higher iron con­
support [10]. However, in most other studies first-order kinetics were
tent are much softer compared to those with lower iron content. The
found to have a better correlation. So, first-order kinetic plot was also
presence of higher amount of iron oxide causes the beads to be weak and
tried out in our case using the experimental data. However, the corre­
hence during the reaction it breaks. So, from an economic and practical
lation for zero-order kinetics was better than that of the first-order ki­
point of view, the beads with lower iron content are recommended,
netics (Fig. S8). It is important to note that, in the present case the
although the beads with higher iron loading show better catalytic per­
iron-oxide embedded in Alg-ben beads in-situ converted to ZVI (FGME)
formance. In the present work, the beads with lesser iron content are
during the borohydride reduction of 4-NP, and acted as a catalyst. This is
chosen for 4-NP reduction.
also corroborated from the induction time required for the catalysis.
During the process, 4-NP was gradually reduced to 4-AP and the
3.4. Reusability of the catalyst
absorbance value at 400 nm gradually decreased with the concurrent
appearance of a new peak at 293 nm due to 4-AP. After a certain time
From a practical point of view, a catalyst should be reusable to
period, the absorbance value at 400 nm became almost constant and
minimize the cost and to make the process more acceptable. The reus­
again a parallel line with respect to the time axis was obtained. In the
ability of the catalyst has been examined by adding the same amount of
present study, the point at which the reduced absorbance became almost
4-NP to the existing solution after one run. It is interesting to observe
constant was considered as the end of the reaction. Using the calibration
here that during the first cycle the total time taken to reduce 4-NP
curve of the 4-nitrophenolate ion (mentioned in Section 2.3.2 and
(~90%) is about 10 min while in the next cycles the time of reaction

6
S. Biswas and A. Pal Materials Today Communications 28 (2021) 102588

experiments of the 4-NP reduction using the hydrogel beads, the in­
duction time varies. Variation in the induction time may be due to the
non-uniformity in the matrix structure. The results of reproducibility
studies are summarised in Table S4.

3.6. Effect of temperature on 4-NP reduction

The surrounding temperature often plays an important role in gov­

Fig. 5. Graphical representation of accumulation of 4-AP in consecutive cycles.
[4-NP] = 60 µM, dose = 0.84 g/L.
erning the kinetics of chemical reactions. So, to have an insight
regarding the influence of environmental temperature on 4-NP reduc­
tion, three temperatures (293 K, 303 K, and 313 K) were considered.
The experiments have been conducted using a catalyst dose of 0.84 g/L
and 4-NP concentration 60 µM., and finally, lnk vs. 1/T is plotted
(Fig. 6). It is observed that with the increase of temperature the rate
constant increases which is quite obvious. It is noteworthy that, in all
cases, zero-order kinetics is followed.
The aim of carrying out the 4-NP reduction at different temperatures
is to calculate the activation energy of the reaction. Activation energy is
defined as the minimum energy which a reacting species must possess to
perform certain chemical reaction. According to the Arrhenius equation,
the activation energy can be written mathematically as.
k=Ae-Ea/RT

where k is the zero-order reaction rate constant (mol/l/s), A is the

is even shorter. It may be because in the first cycle the loaded iron oxide Arrhenius factor, Ea is the activation energy of the reaction (cal/mol), T
takes some time to get converted to ZVI in the borohydride environment. is the temperature in K and R is the universal gas constant (1.98 cal/
But in the consecutive cycles already formed, ZVI rapidly starts its cat­ Kmol).
alytic activity to reduce 4-NP, and no induction time is required. If the From the slope of the straight line (plot of lnk vs. 1/T) Ea is calcu­
induction time is subtracted from the total time of reduction then the lated. In the present work, Ea is found to be around 16 kcal/mol.
conversion of 4-NP to 4-AP would have been completed within 2.5 min. However, generally for surface catalyzed reactions the value lies within
Various biopolymer hydrogel-based catalysts have been reported so far 2–10 kcal/mol. In literature higher activation energy has also been re­
to reduce 4-NP to 4-AP [15,57]. It is quite encouraging to note that even ported for 4-NP reduction [62,63]. However, in such cases, the order of
after 5 cycles, the Io-alg-ben shows almost same (~90%) degradation the reaction is not zero order.
efficiency as that of the first cycle which makes the catalyst more sus­
tainable and economical.
As the aim of the reduction of 4-NP is the generation of 4-AP, it was
felt pertinent to monitor the concentration of 4-AP in the successive
cycles. As the cycle goes on, there is a successive increase in the
absorbance value at 293 nm (designated peak for 4-AP), which indicates
clearly that the newly added 4-NP in the consecutive cycles produces 4-
AP, and it gradually gets accumulated in the reaction mixture. The re­
sults are shown graphically in Fig. 5. A comparative account on the
performance of the biopolymer-based catalysts for 4-NP reduction has
been presented in Table 2.

3.5. Reproducibility studies for the 4-NP reduction using Io-alg-ben

hydrogel bead catalyst

It is mandatory to have an idea about the reproducibility of the data.

Thus, three repetitive kinetic experiments have been conducted using
the catalyst Io-alg-ben keeping the operating conditions same, and
finally, the rate constant values (k′ , k’’ and k’’’) for the three repetitive
experiments are compared. Earlier, only a few attempts have been made
to check the reproducibility of 4-NP reduction. It is noted in our work
Fig. 6. Plot of lnk vs. 1/T for 4-NP reduction using the catalyst Io-alg-ben. [4-
that the rate constant values vary within ± 10% of their mean value
NP] = 60 µM, dose = 0.84 g/L.
(Table S4). However, it is observed that, during the repetitive

Table 2
Comparison of performance of various biopolymer-based catalysts toward 4-NP reduction.
Biopolymer-based catalyst Order of reaction Rate constant Time of reaction Cycles Reference
1
Agar copper oxide nanocomposite (Ag-CuO) Pseudo- First 0.401 min− 10 min 5 [58]
Ag0 loaded on open pores polyurethane sponge coated with agarose (Ag/AG-OPPUS) Pseudo- First 0.752 min− 1
7 min 3 [59]
AgNPs supported on titanate nanosheet (clAP/exfLT-AgNPs) – 16 s 16 [60]
AgNPs embedded in gelatin biopolymer hydrogels (Ag-GL) Pseudo- First 0.621 min− 1 6 min 3 [61]
Iron oxide-alginate-bentonite hydrogel beads (Io-alg-ben) Zero 22.58 × 10− 6 M min− 1
12 min 5 This work

7
S. Biswas and A. Pal Materials Today Communications 28 (2021) 102588

Table 3
Comparison of TON (turnover number) and TOF (turnover frequency) of various catalysts for 4-NP reduction.
Catalyst TON TOF Reference
− 1
CuFe2O4 magnetic nanoparticles – 0.2 s [1]
Au supported on SMS (surfactant modified silica) 1.2 × 1023molecules/g 20.07 × 1019molecules/g/s [8]
Ag, Au supported on alginate – 9.3 × 1016molecules/g/s, 1.7 × 1016molecules/g/s [10]
Ag loaded on TP rhizome powder 19.2 3.846 min− 1 [11]
AuNPs-HG (Gold nanoparticles gelatin hydrogel composite) 11.9 21 h− 1 [18]
Ni loaded on SDS modified chitosan beads 3.0115 × 1019 molecules/g 5.019 × 1016molecules/g/s [19]
CuO/ZnO nanocomposite 7.53 × 1021molecules/g 4.18 × 1019molecules/g/s [36]
Cu/RGO/Fe3O4 nanocomposite 6.023 × 1021 molecules/g 3.088 × 1019 molecules/g/s [54]
Natrolite zeolite/ Pd nanocomposite 1.07 × 1022 molecules/g 2.15 × 1020molecules/g/s [64]
Ag/RGO nanocomposite 5.37 × 1021molecules/g 2.44 × 1019molecules/g/s [65]
CoFe2O4 nanoparticles 5.37 × 1021molecules/g 1.79 × 1018molecules/g/s [66]
SiO2@Fe3O4/C@Au composites 17.4 min− 1 [67]
Ag nanoparticles decorated on Co3O4 porous sheets 22 h− 1 [68]
Io-alg-ben 4.3 × 1019molecules/g 3.09 × 1017molecules/g/s This work

Fig. 7. Photographic images of Io-alg-ben hydrogel beads after completion of 4-NP reduction. The beads were separated from the reaction mixture and kept in a petri
dish and waited for different times. (a) 0 time, (b) 30 min, (c) 60 min, (d) 120 min.

3.7. Comparison of the turnover number (TON) and turnover frequency catalyst for 4-NP reduction.
(TOF) of Io-alg-ben catalyst with other reported catalysts

The efficiency of the catalyst is obtained from the TON and TOF of a
catalytic process. The TON and TOF of the catalyst Io-alg-ben have been
calculated and found to be 4.3 × 1019 molecules/g and
3.09 × 1017molecules/g/s (induction time not considered), respec­
tively. The TON and TOF values of some other reported catalysts used
for 4-NP reduction have been compiled in Table 3. The TOF and TON
values for Io-alg-ben have been calculated for the 4-NP reduction at a
concentration of 60 µM and at a catalyst dose of 0.84 g/L. The values are
quite comparable to those obtained for other catalysts. This indicates
that the as-prepared Io-alg-ben hydrogel beads can serve as an efficient
3.8. Fate and sustainability of the catalyst after 4-NP reduction
Most of the previous reports on 4-NP reduction did not highlight on
the fate and condition of the catalyst after the reaction. From an envi­
ronmental point of view, it is very important to know the ultimate state
of the catalyst, since nanoparticles which are often used for remediation
of environmental pollution, themselves become pollutants after
disposal. To have an insight, the hydrogel beads after the 4-NP reduc­
tion, are taken out and kept in a petri dish under the ambient condition
for further observation. It has been already stated that in borohydride
condition all the loaded iron oxide get converted to Fe(0) due to which

8
S. Biswas and A. Pal
hydrogel beads become black. However, as time elapsed the brown color
gradually re-appeared on the surface of the beads (shown in Fig. 7). It is
because ZVI is very much reactive and under the normal atmospheric
condition it is rapidly converted to iron oxide. In our work characteri­
sation analysis outside the borohydride environment in dry state has not
been attempted as it would not be able to define the true catalytic
environment. The photographic images (Fig. 7) show the colour change
taking place with time. At the end of 2 h, the beads become brown as it
looked at the start of the reaction. However, the morphology of the
beads before the start of the reaction and after two hours since the end of
the reaction are not the same. With the gradual loss of moisture, they
become deformed and get somewhat sticky.
4. Conclusions
Several alginate-based hydrogel beads were prepared for their cat­
alytic application in 4-NP reduction by NaBH4. Among all the beads,
iron oxide-loaded alginate (Io-alg) and iron oxide-loaded alginate
bentonite (Io-alg-ben) beads showed efficient catalytic behaviour. The
embedded iron oxide was in-situ converted step-wise to growing and
fully grown microelectrode of zero-valent iron (ZVI) under NaBH4
condition, which was the actual catalyst. The alginate and alginate-
bentonite hydrogel bead support have the potential to offer better sta­
bilization to the ZVI catalyst. Because of higher mechanical strength due
to presence of bentonite Io-alg-ben catalyst was recommended. The ef­
fects of various environmental conditions such as the initial concentra­
tion of 4-NP, dose of the catalyst, etc. have been examined. The 4-NP
reduction followed zero-order kinetics. The TON and TOF values of the
Io-alg-ben catalyst are 4.3 × 1019 molecules/g and 3.09 × 1017 mole­
cules/g/s, respectively. In conclusion, a green and sustainable iron-
loaded alginate-bentonite composite hydrogel bead has been synthe­
sized, characterized, and finally has been used as a catalyst toward 4-NP
reduction in borohydride condition. The material is proved to be very
efficient, economical and recycle able.
CRediT authorship contribution statement
Subhadeep Biswas: Conceptualization, Methodolody, Data cura­
tion, Writing - original draft, Investigation. Anjali Pal: Supervision,
Writing - review & editing, Conceptualization.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of an ongoing study.
Acknowledgments
Authors are thankful to IIT Kharagpur for providing the instrumental
facility and Ministry of Education, Government of India, for financial
support.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.mtcomm.2021.102588.
9
Materials Today Communications 28 (2021) 102588
References
[1] J. Feng, L. Su, Y. Ma, C. Ren, Q. Guo, X. Chen, CuFe2O4 magnetic nanoparticles: a
simple and efficient catalyst for the reduction of nitrophenol, Chem. Eng. J. 221
(2013) 16–24, https://doi.org/10.1016/j.cej.2013.02.009.
[2] A. Adak, A. Pal, M. Bandyopadhyay, Removal of phenol from water environment
by surfactant-modified alumina through adsolubilization, Colloids Surf. A 277
(2006) 63–68, https://doi.org/10.1016/j.colsurfa.2005.11.012.
[3] A. Dabrowski, P. Podkoscielny, Z. Hubicki, M. Barczak, Adsorption of phenolic
compounds by activated carbon-a critical review, Chemosphere 58 (2005)
1049–1070, https://doi.org/10.1016/j.chemosphere.2004.09.067.
[4] M. Ahmaruzzaman, Adsorption of phenolic compounds on low cost adsorbents: a
review, Adv. Colloid Interface Sci. 143 (2008) 48–67, https://doi.org/j.
cis.2008.07.002.
[5] H. Koga, T. Kitaoka, One-step synthesis of gold nanocatalysts on a microstructured
paper matrix for the reduction of 4-nitrophenol, Chem. Eng. J. 168 (2011)
420–425, https://doi.org/10.1016/j.cej.2010.08.073.
[6] N. Pradhan, A. Pal, T. Pal, Catalytic reduction of aromatic nitro compounds by
coinage metal nanoparticles, Langmuir 17 (2001) 1800–1802, https://doi.org/
10.1021/la000862d.
[7] N. Pradhan, A. Pal, T. Pal, Silver nanoparticle catalyzed reduction of aromatic nitro
compounds, Colloids Surf. A. 196 (2002) 247–257, https://doi.org/10.1016/
S0927-7757(01)01040-8.
[8] P. Mahamallik, A. Pal, A soft-template mediated approach for Au(0) formation on a
heterosilica surface and synergism in the catalytic reduction of 4-nitrophenol, RSC
Adv. 5 (2015) 78006–78016, https://doi.org/10.1039/C5RA16655A.
[9] S. Manivannan, B. Krishnakumari, R. Ramaraj, Synthesis of silicate sol-gel matrix
embedded silver nanostructures: efficient nanocatalyst for the reduction of 4-
nitrophenol, Chem. Eng. J. 204- 206 (2012) 16–22, https://doi.org/10.1016/j.
cej.2012.07.092.
[10] S. Saha, A. Pal, S. Kundu, S. Basu, T. Pal, Photochemical green synthesis of calcium-
alginate-stabilized Ag and Au nanoparticles and their catalytic application to 4-
Nitrophenol reduction, Langmuir 26 (2010) 2885–2893, https://doi.org/10.1021/
la902950x.
[11] M. Ismail, M.I. khan, S.B. Khan, K. Akhtar, M.A. Khan, A.M. Asiri, Catalytic
reduction of picric acid, nitrophenols and organic azo dyes via green synthesized
plant supported Ag nanoparticles, J. Mol. Liq. 268 (2018) 87–101, https://doi.org/
10.1016/j.molliq.2018.07.030.
[12] R. Rarima, G. Unnikrishnan, Porous poly (lactic acid)/ nano-silver composite
membranes for catalytic reduction of 4-nitrophenol, Mater. Chem. Phys. 241
(2020), 122389, https://doi.org/10.1016/j.matchemphys.2019.122389.
[13] F. Torkamani, S. Azizian, Green and simple synthesis of Ag nanoparticles loaded
onto cellulosic fiber as efficient and low-cost catalyst for reduction of 4-
nitrophenol, J. Mol. Liq. 214 (2016) 270–275, https://doi.org/10.1016/j.
molliq.2015.12.071.
[14] M.K. Guria, M. Majumdar, M. Bhattacharyya, Green synthesis of protein capped
gold nano-gold particle: An excellent recyclable nano-catalyst for the reduction of
nitro-aromatic pollutants at higher concentration, J. Mol. Liq. 222 (2016)
549–557, https://doi.org/10.1016/j.molliq.2016.07.087.
[15] L. Ai, J. Jiang, Catalytic reduction of 4-nitrophenol by silver nanoparticles
stabilized on environmentally benign macroscopic biopolymer hydrogel,
Bioresour. Technol. 132 (2013) 374–377, https://doi.org/10.1016/j.
biortech.2012.10.161.
[16] F. Liu, X. Liu, W. Liu, H. Gu, ROMP synthesis of gallol-containing polymer
hydrogels for in-situ fabrication of AuNPs and AgNPs composites as recyclable
catalysts for the degradation of 4-nitrophenol, Polymer 219 (2021), 123539,
https://doi.org/10.1016/j.polymer.2021.123539.
[17] Q. Zhao, S. Mu, X. Liu, G. Qiu, D. Astruc, H. Gu, Gallol-tethered injectable AuNP
hydrogel with desirable self-healing and catalytic properties, Macromol. Chem.
Phys. 220 (2019) 1800427, https://doi.org/10.1002/macp.201800427.
[18] Y. Long, B. Song, C. Shi, W. Liu, H. Gu, AuNPs composites of gelatin hydrogels
crosslinked by ferrocene-containing polymer as recyclable supported catalysts,
J. Appl. Pol. Sci. 137 (2020) 48653, https://doi.org/10.1002/APP48653.
[19] R.J. Kongarapu, P. Mahamallik, A. Pal, Surfactant modification of chitosan
hydrogel beads for Ni@NiO core-shell nanoparticles formation and its catalysis to
4-nitrophenol reduction, J. Environ. Chem. Eng. 5 (2017) 1321–1329, https://doi.
org/10.1016/j.jece.2017.02.017.
[20] N. Sahiner, H. Ozay, O. Ozay, N. Aktas, New catalytic route: Hydrogels as
templates and reactors for in situ Ni nanoparticle synthesis and usage in the
reduction of 2- and 4- nitrophenols, Appl. Catal. A Gen. 385 (2010) 201–207,
https://doi.org/10.1016/j.apcata.2010.07.004.
[21] M. Blosi, S. Albonetti, A.L. Costa, N. Sangiorgi, A. Sanson, Easily scalable synthesis
of Ni nanosols suitable for the hydrogenation of 4-nitrophenol to p-aminophenol
under mild condition, Chem. Eng. J. 215–216 (2013) 616–625, https://doi.org/
10.1016/j.cej.2012.11.013.
[22] P. Zhang, Y. Sui, G. Xiao, Y. Wang, C. Wang, B. Liu, G. Zou, B. Zou, Facile
fabrication of faceted copper nanocrystals with high catalytic activity for p-
nitrophenol reduction, J. Mater. Chem. A 1 (2013) 1632–1638, https://doi.org/
10.1039/C2TA00350C.
[23] A.A. Nafiey, A. Addad, B. Sieber, G. Chastanet, A. Barras, S. Szunerits,
R. Boukherroub, Reduced graphene oxide decorated with Co3O4 nanoparticles
(rGO-Co3O4) nanocomposite: a reusable catalyst for highly efficient reduction of 4-
nitrophenol, and Cr(VI) and dye removal from aqueous solutions, Chem. Eng. J.
322 (2017) 375–384, https://doi.org/10.1016/j.cej.2017.04.039.
[24] M.S. Bashir, X. Jiang, X.Z. Kong, Porous polyurea microspheres with Pd
immobilized on surface and their catalytic activity in 4-nitrophenol reduction and
S. Biswas and A. Pal
organic dyes degradation, Eur. Polym. J. 129 (2020), 109652, https://doi.org/
10.1016/j.eurpolymj.2020.109652.
[25] D. Ayodhya, G. Veerabhadram, Stable and efficient graphitic carbon nitride
nanosheet-supported ZnS composite catalysts toward competent catalytic
performance for the reduction of 4-nitrophenol using NaBH4, Mat. Today Sus. 5
(2019), 100015, https://doi.org/10.1016/j.mtsust.2019.100015.
[26] M.S.J. Khan, T. Kamal, F. Ali, A.M. Asiri, S.B. Khan, Chitosan-coated polyurethane
sponge supported metal nanoparticles for catalytic reduction of organic pollutants,
Int. J. Biol. Macromol. 132 (2019) 772–783, https://doi.org/10.1016/j.
ijbiomac.2019.03.205.
[27] C. Gao, X. Wang, S. Zhai, Q. An, Enhanced catalytic activity of nanosilver with
lignin/ polyacrylamide hydrogel for reducing p-nitrophenol, Int. J. Biol. Macromol.
134 (2019) 202–209, https://doi.org/10.1016/j.ijbiomac.2019.05.017.
[28] C. Gao, X. Wang, H. Wang, J. Zhou, S. Zhai, Q. An, Highly efficient and stable
catalysis of p-nitrophenol via silver/ lignin/ polyacrylic acid hydrogel, Int. J. Biol.
Macromol. 144 (2020) 947–953, https://doi.org/10.1016/j.ijbiomac.2019.09.172.
[29] P.D. Tomke, V.K. Rathod, Facile fabrication of silver on magnetic nanocomposite
(Fe3O4@Chitosan-AgNP nanocomposite) for catalytic reduction of anthropogenic
pollutant and agricultural pathogens, Int. J. Biol. Macromol. 149 (2020) 989–999,
https://doi.org/10.1016/j.ijbiomac.2020.01.183.
[30] S. Bae, S. Gim, H. Kim, K. Hanna, Effect on NaBH4 on properties of nanoscale zero-
valent iron and its catalytic activity for reduction of p-nitrophenol, Appl. Catal. B
Environ. 182 (2016) 541–549, https://doi.org/10.1016/j.apcatb.2015.10.006.
[31] V.K. Gupta, M.L. Yola, T. Eren, F. Kartal, M.O. Caglayan, N. Atar, Catalytic activity
of Fe@Ag nanoparticle involved calcium alginate beads for the reduction of
nitrophenols, J. Mol. Liq. 190 (2014) 133–138, https://doi.org/10.1016/j.
molliq.2013.10.022.
[32] B. Lai, Y. Zhang, R. Li, Y. Zhou, J. Wang, Influence of operating temperature on the
reduction of high concentration of p-nitrophenol (PNP) by zero valent iron (ZVI),
Chem. Eng. J. 249 (2014) 143–152, https://doi.org/10.1016/j.cej.2014.03.108.
[33] L. Tang, J. Tang, G. Zeng, G. Yang, X. Xie, Y. Zhou, Y. Pang, Y. Fang, J. Wang,
W. Xiong, Rapid reductive degradation of aqueous p-nitrophenol using nanoscale
zero-valent iron particles immobilized on mesoporous silica with enhanced
antioxidation effect, Appl. Surf. Sci. 333 (2015) 220–228, https://doi.org/
10.1016/j.apsusc.2015.02.025.
[34] K. Sravanthi, D. Ayodhya, P.Y. Swamy, Green synthesis, characterization and
catalytic activity of 4-nitrophenol reduction and formation of benzimidazoles using
bentonite supported zero valent iron nanoparticles, Mater. Sci. Energy Technol. 2
(2019) 298–307, https://doi.org/10.1016/j.mset.2019.02.003.
[35] M. Maryami, M. Nasrollahzadeh, E. Mehdipour, S.M. Sajadi, Green synthesis of the
Pd/perlite nanocomposite using Euphorbia neriifolia L. leaf extract and evaluation
of its catalytic activity, Sep. Purif. Technol. 184 (2017) 298–307, https://doi.org/
10.1016/j.seppur.2017.05.003.
[36] M. Bordbar, N. Negahdar, M. Nasrollahzadeh, Melissa officinalis L. leaf extract
assisted green synthesis of CuO/ZnO nanocomposite for the reduction of 4-nitro­
phenol and Rhodamine B, Sep. Purif. Technol. 191 (2018) 295–300, https://doi.
org/10.1016/j.seppur.2017.09.044.
[37] A. Pal, K. Esumi, T. Pal, Preparation of nanosized gold particles in a biopolymer
using UV photoactivation, J. Colloid Interf. Sci. 288 (2005) 396–401, https://doi.
org/10.1016/j.jcis.2005.03.048.
[38] A.N. Bezbaruah, S. Krajangpan, B.J. Chrisholm, E. Khan, J.J.E. Bermudez,
Entrapment of iron nanoparticles in calcium alginate beads for groundwater
remediation applications, J. Hazard. Mater. 166 (2009) 1339–1343, https://doi.
org/10.1016/j.jhazmat.2008.12.054.
[39] J.P. Ibanez, Y. Umetsu, Potential of protonated alginate beads for heavy metals
uptake, Hydrometallurgy 64 (2002) 89–99, https://doi.org/10.1016/S0304-386X
(02)00012-9.
[40] R. Banda, T.H. Nguyen, S.H. Sohn, M.S. Lee, Recovery of valuable metals and
regeneration of acid from the leaching solution of spent HDS catalysts by solvent
extraction, Hydrometallurgy 133 (2013) 161–167, https://doi.org/10.1016/j.
hydromet.2013.01.006.
[41] Y. Yukselen, A. Kaya, Suitability of the methylene blue test for surface area, cation
exchange capacity and swell potential determination of clayey soils, Eng. Geol. 102
(2008) 38–45, https://doi.org/10.1016/j.enggeo.2008.07.002.
[42] A.F. Hassan, A.M. Abdel-Mohsen, M.M.G. Fouda, Comparative study of calcium
alginate. activated carbon, and their composite beads on methylene blue
adsorption, Carbohydr. Polym. 102 (2014) 192–198, https://doi.org/10.1016/j.
carbpol.2013.10.104.
[43] J. Luo, S. Bo, Y. Qin, Q. An, Z. Xiao, S. Zhai, Multistage reclamation of Co2+-
containing alginate hydrogels as excellent reduction catalyst and subsequent
microwave absorber by facile transformation, Int. J. Biol. Macromol. 106 (2021)
1513–1525, https://doi.org/10.1016/j.ijbiomac.2020.11.031.
[44] S. Wunder, F. Polzer, Y. Lu, Y. Mei, M. Ballauff, Kinetic analysis of catalytic
reduction of 4-nitrophenol by metallic nanoparticles immobilized in spherical
polyelectrolyte brushes, J. Phys. Chem. C 114 (2010) 8814–8820, https://doi.org/
10.1021/jp101125j.
[45] S. Gu, Y. Lu, J. Kaiser, M. Albrecht, M. Ballauff, Kinetic analysis of the reduction of
4-nitrophenol catalyzed by Au/Pd nanoalloys immobilized in spherical
polyelectrolyte brushes, Phys. Chem. Chem. Phys. 17 (2015) 28137–28143,
https://doi.org/10.1039/C5CP00519A.
[46] Y. Nakatsuji, Z. Salehi, Y. Kawase, Mechanisms for removal of p-nitrophenol from
aqueous solution using zero-valent iron, J. Environ. Manag. 152 (2015) 183–191,
https://doi.org/10.1016/j.jenvman.2015.01.012.
10
Materials Today Communications 28 (2021) 102588
[47] S. Kundu, A. Pal, A.K. Dikshit, UV induced degradation of herbicide 2,4-D: Kinetics,
mechanism and effect of various conditions on the degradation, Sep. Purif.
Technol. 44 (2005) 121–129, https://doi.org/10.1016/j.seppur.2004.12.008.
[48] P. Kumararaja, K.M. Manjaiah, S.C. Datta, T.P.A. Shabeer, B. Sarkar, Chitosan-g-
poly (acrylic acid)-bentonite composite: a potential immobilizing agent of heavy
metals in soil, Cellulose 25 (2018) 3985–3999, https://doi.org/10.1007/s10570-
018-1828-x.
[49] Z. Chi, Z. Wang, H. Chu, P. Bin, L. Lucian, Bentonite-supported nanoscale zero-
valent iron granulated electrodes for industrial wastewater remediation, RSC Adv.
7 (2017) 44605–44613, https://doi.org/10.1039/C7RA07584G.
[50] Z. Diao, X. Xu, D. Jiang, L. Kong, Y. Sun, Y. Hu, Q. Hao, H. Chen, Bentonite-
supported nanoscale zero-valent iron/persulfate system for the simultaneous
removal of Cr(VI) and phenol from aqueous solutions, Chem. Eng. J. 302 (2016)
213–222, https://doi.org/10.1016/j.cej.2016.05.062.
[51] H. Lu, X. Qiao, W. Wang, F. Tan, Z. Xiao, J. Chen, Chitosan stabilised nanozero-
valent iron for the catalytic reduction of p-nitrophenol, Micro Nano Lett. 9 (2014)
446–450, https://doi.org/10.1049/mnl.2014.0117.
[52] C. Karthikeyan, M. Ranjani, A.R. Kim, D.J. Yoo, G.G. Kumar, Synthesis of iron
nanoparticles using Azadirachta indica extract and its catalytic activity toward
nitrophenol reduction, J. Nanosci. Nanotechnol. 16 (2016) 2527–2533, https://
doi.org/10.1166/jnn.2016.10793.
[53] K. Sravanthi, D. Ayodhya, P.Y. Swamy, Green synthesis, characterization of
biomaterial-supported zero-valent iron nanoparticles for contaminated water
treatment, J. Anal. Sci. Technol. 9 (2018) 1–11, https://doi.org/10.1186/s40543-
017-0134-9.
[54] M. Atarod, M. Nasrollahzadeh, S.M. Sajadi, Green synthesis of a Cu/reduced
graphene oxide/Fe3O4 nanocomposite using Euphorbia wallichii leaf extract and its
application as a recyclable and heterogeneous catalyst for the reduction of 4-
nitrophenol and Rhodamine B, RSC Adv. 5 (2015) 91532–91543, https://doi.org/
10.1039/C5RA17269A.
[55] M. Xia, S. Kang, G. Lee, Y.S. Huh, B.J. Park, The recyclability of alginate hydrogel
particles as a palladium catalyst support, J. Ind. Eng. Chem. 73 (2019) 306–315,
https://doi.org/10.1016/j.jiec.2019.01.042.
[56] H. Zhang, Y. Shi, X. Xu, M. Zhang, L. Ma, Structure regulation of Alginate-
Bentonite nanocomposites for controlled release of Imidacloprid, ACS Omega 5
(2020) 10068–10076, https://doi.org/10.1021/acsomega.0c00610.
[57] L. Ai, H. Yue, J. Jiang, Environmentally friendly light-driven synthesis of Ag
nanoparticles in situ grown on magnetically separable biohydrogels as highly
active and recyclable catalysts for 4-nitrophenol reduction, J. Mater. Chem. 22
(2012) 23447–23453, https://doi.org/10.1039/c2jm35616c.
[58] T. Kamal, Aminophenols formation from nitrophenols using agar biopolymer
hydrogel supported CuO nanoparticles catalyst, Polym. Test. 77 (2019), 105896,
https://doi.org/10.1016/j.polymertesting.2019.105896.
[59] M.S.J. Khan, S.B. Khan, T. Kamal, A.M. Asiri, Agarose biopolymer coating on
polyurethane sponge as host for catalytic silver metal nanoparticles, Polym. Test.
78 (2019), 105983, https://doi.org/10.1016/j.polymertesting.2019.105983.
[60] A.K. Sarkar, A. Saha, L. Midya, C. Banerjee, N. Mandre, A.B. Panda, S. Pal, Cross-
linked biopolymer stabilized exfoliate titanate nanosheet-supported AgNPs: a
green sustainable ternary nanocomposite hydrogel for catalytic and antimicrobial
activity, ACS Sustain, Chem. Eng. 5 (2017) 1881–1891, https://doi.org/10.1021/
acssuschemeng.6b02594.
[61] T. Kamal, M.S.J. Khan, S.B. Khan, A.M. Asiri, M.T.S. Chani, M.W. Ullah, Silver
nanoparticles embedded in gelatin biopolymer hydrogel as catalyst for reductive
degradation of pollutants, J. Polym. Environ. 28 (2020) 399–410, https://doi.org/
10.1007/s10924-019-01615-8.
[62] S. Chairam, W. Konkamdee, R. Parakhun, Starch-supported gold nanoparticles and
their use in 4-nitrophenol reduction, J. Saudi Chem. Soc. 21 (2017) 656–663,
https://doi.org/10.1016/j.jscs.2015.11.001.
[63] Z.M. El-Bahy, Preparation and characterization of Pt-promoted NiY and CoY
catalysts employed for 4-nitrophenol reduction, Appl. Catal. A 468 (2013)
175–183, https://doi.org/10.1016/j.apcata.2013.08.047.
[64] A. Hatamifard, M. Nasrollahzadeh, J. Lipkowski, Green synthesis of a natrolite
zeolite/palladium nanocomposite and its application as a reusable catalyst for the
reduction of organic dyes in a very short time, RSC Adv. 5 (2015) 91372–91381,
https://doi.org/10.1039/C5RA18476B.
[65] M. Maryami, M. Nasrollahzadeh, E. Mehdipour, S.M. Sajadi, Preparation of the Ag/
RGO nanocomposite by use of Abutilon hirtum leaf extract: a recoverable catalyst
for the reduction of organic dyes in aqueous medium at room temperature, Int. J.
Hydrog. Energy 41 (2016) 21236–21245, https://doi.org/10.1016/j.
ijhydene.2016.09.130.
[66] M. Nasrollahzadeh, M. Bagherzadeh, H. Karimi, Preparation, characterization and
catalytic activity of CoFe2O4 nanoparticles as a magnetically recoverable catalyst
for selective oxidation of benzyl alcohol to benzaldehyde and reduction of organic
dyes, J. Colloid Interf. Sci. 465 (2016) 271–278, https://doi.org/10.1016/j.
jcis.2015.11.074.
[67] T. Zeng, X. Zhang, S. Wang, Y. Ma, H. Niu, Y. Cai, A double-shelled yolk-like
structure as an ideal magnetic support of tiny gold nanoparticles for nitrophenol
reduction, J. Mat. Chem. A 1 (2013) 11641–11647, https://doi.org/10.1039/
C3TA12660A.
[68] J. Liu, J. Li, R. Meng, P. Jian, L. Wang, Silver nanoparticles-decorated-CO3O4
porous sheets as efficient catalysts for the liquid-phase hydrogenation reduction of
p-Nitrophenol. J, Colloid Interf. Sci. 551 (2019) 261–269, https://doi.org/
10.1016/j.jcis.2019.05.018.