Journal of Environmental Science and Health, Part A

Toxic/Hazardous Substances and Environmental Engineering

ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/lesa20

Polyethylene glycol-modified mesoporous

zerovalent iron nanoparticle as potential catalyst
for improved reductive degradation of Congo red
from wastewater

Ipsita Som, Mouni Roy & Rajnarayan Saha

To cite this article: Ipsita Som, Mouni Roy & Rajnarayan Saha (2023): Polyethylene glycol-
modified mesoporous zerovalent iron nanoparticle as potential catalyst for improved reductive
degradation of Congo red from wastewater, Journal of Environmental Science and Health, Part
A, DOI: 10.1080/10934529.2023.2215679

To link to this article: https://doi.org/10.1080/10934529.2023.2215679

Published online: 26 May 2023.

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JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A
https://doi.org/10.1080/10934529.2023.2215679

Polyethylene glycol-modified mesoporous zerovalent iron nanoparticle as

potential catalyst for improved reductive degradation of Congo red from
wastewater
Ipsita Soma , Mouni Royb, and Rajnarayan Sahaa
a
Department of Chemistry, National Institute of Technology, Durgapur, India; bDepartment of Chemistry, Banasthali University, Banasthali,
Rajasthan, India

ABSTRACT ARTICLE HISTORY

In this study, bare zero-valent iron nanoparticles (nZVI) have been modified using polyethylene Received 2 February 2023
glycol (PEG) of various molecular weight in a facile technique. The synthesized nZVI modified Accepted 10 May 2023
with PEG, M.W. of 600 and 6000 was denoted by nZVI-PEG600 and nZVI-PEG6000, respectively, and
KEYWORDS
compared their catalytic activity towards the reductive degradation of Congo red (CR) using
Zerovalent iron nanoparticle
NaBH4.The existence of PEG layer surrounds the nZVI core was confirmed by several characteriza- (nZVI); polyethylene glycol
tion tools, such as XRD, FTIR, FESEM and TEM. Herein, both nZVI-PEG600 and nZVI-PEG6000 exhib- modified; Congo red;
ited remarkable removal efficiencies of 89.6% and 99.2% within 14 min of reaction time. The reductive degradation;
optimum reaction parameters were found to be as follows: 0.2 g L
1 catalyst dose and initial dye catalytic activity
concentration of 2  10
5 molL
1 etc. Kinetic studies of dye degradation were investigated which
follow pseudo-1st-order kinetics. The TOC analysis confirmed the complete mineralization of CR
dye by nZVI-PEG6000 nanocatalyst. GCMS analysis of plausible degraded products was performed
to elucidate a probable mechanistic pathway of CR degradation. Further, we have investigated the
degradation of two anionic dyes mixture, i.e., CR and methyl orange (MO) using best catalyst, i.e.,
nZVI-PEG6000.

Introduction nontoxicity, cheap.[7–9] nZVI can also be easily separated by

Over the last several decades organic dyes, used enormously in
different industries for instance dyeing, textile, printing, lea-
ther, pharmaceuticals, rubber, cosmetics, plastic, drugs are
acquired major global attention.[1] These organic dyes, dis-
charged continuously into the environmental water bodies
from industries, cause a perilous effect into the ecosystem due
to their potential toxicity, mutagenic, teratogenic and carcino-
genic properties.[2] Thereupon, to address this issue the effi-
cient removal and/or reduction of these harmful contaminants
become the paramount goal by scientists.
In the last few years, numerous techniques have been
developed for the removal of recalcitrant dyes.[3] However,
the catalytic reduction has been emerged as beneficial over
other approaches due to its cost-effectiveness, short reaction
time and easy operation.[4,5] In this approach, NaBH4, a
potential reducing agent is used for significant removal of sev-
eral toxic dyes. Congo red (CR) [1-naphthalenesulfonic acid,
3,30 -(4,40 -biphenylenebis (azo)) bis (4-amino) disodium salt],
a highly toxic and carcinogenic anionic dye can be removed
via reductive degradation using suitable nanoparticles which
can act as catalyst.[6] In this context, nanoscale zero-valent
iron (nZVI) is broadly applied in environmental remediation
owing to its several marvellous properties, such as large sur-
face area, ample adsorption sites, high chemical reactivity,
gravity from reaction mixture.[10,11] However, the agglomerat-
ing tendency and easy oxidation of nZVI decrease its disper-
sion in the reaction medium. In addition, the effective contact
of nZVI with the target pollutants is inhibited, which signifi-
cantly drops the removal efficiency.
Recently, chemists have gradually devoted to the develop-
ment of various supporting or stabilizing materials in order to
overcome certain drawbacks of nZVI including strong ten-
dency of agglomeration, rapid passivation or sedimentation
and consequently low reactivity.[12] So, for example carbon
materials, clay minerals, polymeric materials (e.g., alginate,
chitosan, polyvinyl pyrrolidone, etc.), molecular sieves, kaolin-
ite[13,14], bentonite[15], polyaniline[16–18], polyacrylamide[19],
carbon[20,21] have been recognized as well-known supporting
materials to date. As one of the polymeric materials, i.e., poly-
ethylene glycol (PEG), which is hydrophilic, water-soluble,
eco-friendly, nontoxic, biocompatible[22] can be recognized as
a potential modifier of bare nZVI.[23] Current research work
investigated by Tian et al. investigated that PEG (M.W.¼
4,000) stabilized nZVI nanocomposite exhibit highest specific
surface area of 22.77 m2/g compared to two surfactants (e.g.,
sodium dodecyl sulfate and cationic hexadecyl trimethyl
ammonium bromide) modified nZVI. Additionally, this
obtained value was almost three times higher than unmodified
nZVI.[9,24] However, the colloidal stability of nZVI depends

CONTACT Rajnarayan Saha rnsahanitd@gmail.com Department of Chemistry, National Institute of Technology, Durgapur 713209, India
ß 2023 Taylor & Francis Group, LLC
2 I. SOM ET AL.
upon the chain length of PEG. The hydroxyl groups of PEG
molecule can prevent the agglomeration of nanoparticles by
increasing the distance between two NPs. Hence, the steric
repulsion[25] between two individual nanoparticle can strongly
act when the length of PEG chain increases.[26–29] The toxicity
of nZVI can be drastically inhibited after its modification with
PEG.[30] Ergṻt et al., synthesized iron oxide nanoparticles
loaded carbonated hydroxyapatite for degradation of
Malachite Green (MG). The optimum reaction condition was
kept as follow: H2O2 concentration: 30 mM, initial dye concen-
tration: 100 mg L
1 and catalyst concentration 1.0 g L
1. At
the end of the reaction, 100% decolorization efficiency and
33.3% COD removal were achieved.[31] Chen et al. fabricated
Polypyrrole/Attapulgite-supported nanoscale zero-valent iron
(PPy/APT-nZVI) composites for the removal of Napthol
Green B (NGB).[32] In this experiment, 99.59% of NGB was
removed using 1 g L
1 PPy/APT-nZVI (1:0.5) dosage after
25 min reaction time, much higher than attapulgite, polypyr-
role, polypyrrole/attapulgite and bare nZVI at pH 6. The resus-
ability test of PPy/APT-nZVI suggests the potentiality of
PPy/APT-nZVI (1:0.5) for NGB degradation. Sallam et al.
investigated the catalytic degradation of 4-nitrophenol (4-NP)
and 2-nitroaniline (2-NA)by using prepared silver-doped
maghemite (Ag–c-Fe2O3) nanocomposite in presence of
NaBH4.[33] The activity parameters for the reduction of both
4-NP and 2-NA by Ag–c-Fe2O3 nanocomposite were obtained
to be 69.2, and 43.4 s
1 gcat
1, respectively. The result proves
that Ag–c-Fe2O3 is a promising catalyst for the reductions of
nitro aromatic compounds. Subruiti et al., fabricated
MFe2O4/-Fe2O3 nanocomposites (M ¼ Ni or Co) for reduction
of 4-NP, 2-NA and methyl orange (MO).[34] The obtained cat-
alysts, i.e., NiFe2O4/c-Fe2O3 and CoFe2O4/c-Fe2O3 exhibited
improved specific activity parameter of 993.9 and 929.8 s
1,
respectively, towards the reduction of 4-NP. Similarly, 712.2
and 680.9 s
1 specific activity value was achieved for
NiFe2O4/c-Fe2O3 and CoFe2O4/c-Fe2O3 in case of the reduc-
tion of 2-NA.
Despite several work reported[32,35,36] the use of polymer-
modified nZVI nanocomposite to examine the dye degrad-
ation in presence of NaBH4, there have only been a few
comparative studies on the catalytic activity of varying
molecular weight containing PEG-modified nZVI. Herein, as
per our best knowledge, we address for the first time a com-
parative study on the CR dye degradation efficiency of PEG
(with different molecular weight) modified nZVI and bare
nZVI. Therefore, this study mainly exploits (1) synthesis of
novel various molecular weight containing PEG-modified
nZVI via a simple and efficient chemical reduction tech-
nique at room temperature; (2) study on the crucial role of
PEG for the modification of nZVI in terms of their spectro-
scopic, microscopic, and catalytic qualities; (3) Tuning the
several reaction parameters (catalyst dosage, pH, NaBH4
concentration, etc.) in order to improve the removal of CR
dye; (4) identification of intermediates products during cata-
lytic degradation of CR by GCMS analysis. Based on the
GC–MS data, elucidation of a probable reaction mechanistic
pathway was also investigated.
Experimental section
Materials
Anhydrous ferric (III) chloride (FeCl3), sodium borohydride
(NaBH4, 98% purity), Glycerol (C3H8O3, purity > 99.5%), PEG
of MW 6000 and 600 were purchased from Sigma-Aldrich. CR,
MO dye were also acquired from Sigma-Aldrich. Chemical
structures of CR are given in Table A1. Absolute Ethanol
(>99.9%) was obtained from Merck (Bengaluru, India).
Sodium nitrate (NaNO3), Sodium sulfate (Na2SO4) and
Sodium phosphate (Na3PO4) were procured from Merck,
India. All the reagents were used without any additional purifi-
cation. However, all the catalytic experiments were accom-
plished using double distilled water [Sartorious (18.2 MX.cm)].
Synthesis of bare nZVI, PEG-modified nZVI
Bare nZVI was synthesized by following a previously reported
procedure, by one of our works[37] with some modification.
Briefly, 0.73 g of anhydrous FeCl3 was dissolved in 100 mL 3:2
glycerol and water mixture taken in a 500 mL three neck round
bottom flask. The FeCl3 solution was purged with nitrogen for
several minutes to eliminate the dissolved oxygen present in
reaction medium maintaining complete inert atmosphere.
Then, 250 mL 0.25 (M) NaBH4 solution was added dropwise
under nitrogen atmosphere, leading to the appearance of
black-colored particles. After complete addition of NaBH4, the
reaction mixture was stirred for 5 min at 500 rpm to ensure the
completion of reaction. Then, the reaction mixture was trans-
ferred to a 500 mL conical flask to separate the obtained nano-
particles. Thenceforth, the obtained black colored particles
were magnetically separated by using a horseshoe magnet. The
synthesized nZVI particles were washed three times using dou-
ble distilled water and finally absolute ethanol and vacuum
dried at room temperature for overnight. After that, nZVI was
stored in glass vials which are flushed with nitrogen gas prior
to sustain inert atmosphere. The vials are kept in vacuum desic-
cator for further usage. The whole magnetic separation proc-
esses are represented in Figure A2. PEG-modified nZVI was
synthesized by following the similar procedure mentioned
above. Herein, 0.17 mL of PEG (Mw
600) and 0.21 g of PEG
(Mw – 6,000) were added individually after dissolving 0.73 g of
anhydrous FeCl3 in 100 mL 3:2 glycerol and water mixture. The
rest of the method is as similar as the synthesis of bare nZVI.
PEG (Mw 600) and PEG (Mw 6,000) modified nZVI were
denoted as nZVI-PEG600 and nZVI-PEG6000, respectively.
The chemical reaction involved in nZVI synthesis is pre-
sented in Eq. (1). The synthesis procedure of bare nZVI,
nZVI-PEG600 and nZVI-PEG6000 is represented in Scheme 1.
2FeCl3 ðaqÞ þ 6NaBH4 ðaqÞ þ 18H2 O ! 2Fe ðsÞ
(1)
þ 6BðOHÞ3 ðaqÞ þ 6NaCl ðaqÞ þ 21H2 ðgÞ
Characterization
The X-ray diffraction (XRD) studies of the prepared samples
were carried out using Rigaku technologies (Model: Smartlab)

Scheme 1. Synthesis procedure of nanoparticles.
under Ni-filtered Cu-Ka radiation (k ¼ 0.15418 nm) operated
at 9 KW within the 2h range of 20
80 . Scherrer equation
was utilized to determine the crystallite size of the synthesized
samples using the below (Eq. (2)).[38]
Kk
D¼ (2)
bcosh
where D and b imply the average crystallite size and the
full-width half maximum (FWHM) value of the diffraction
peaks respectively, h indicates the Bragg angle and k indi-
cates the wavelength of an incident X-ray. The constant K is
assigned to the crystallite shape generally considered as 0.9
assuming spherical crystals.[34] The characteristic functional
groups present in the samples were confirmed by Thermo
Nicolet iS10 spectrometer using KBr pellets in the range of
4,000
400 cm
1. Brunauer–Emmett–Teller (BET) surface
area was acquired using a NOVA 1000e surface analyzer
from Quantachrome instrument within the relative pressure
(P/P0) range of 0.05–0.20. The morphological studies were
accomplished using a field emission-scanning electron
microscope (Carl Zeiss microscopy Ltd; Model: Sigma-
Aldrich, St. Louis, MO) and a high-resolution transmission
electron microscope (TECHNAI TF20 ST HRTEM, operating
voltage – 10 kV). The selected area electron diffraction
(SAED) pattern of synthesized samples was also recorded.
The EDAX analysis was carried out using Ametek (Model:
Element). X-ray photoelectron spectroscopy (XPS) informa-
tion of bare and PEG-modified nZVI was procured using an
ESCALAB 210 instrument. A nano-series Zetasizer (ZS90),
Malvern instrument was utilized for zeta potential measure-
ment. The UV–visible spectra in the wavelength range of
JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 3
200–800 nm was recorded using a UV–Vis spectrophotom-
eter (Shimadzu IRAffinity-1S WL, Kyoto, Japan).
Catalytic reactions
In a typical catalytic experiment, a fixed amount of as-pre-
pared catalyst was added into 3 mL of reaction solution con-
taining 2  10
5 (M) CR dye in a quartz cuvette (1 cm path
length) which is kept under stirring condition. After that
1 mL of 10 mM NaBH4 solution was rapidly added into the
reaction medium. The red color of the dye solution grad-
ually becomes vanished with increasing the reaction time.
The quartz cuvette was quickly placed in the cell holder of
the spectrophotometer to maintain the accuracy. Therefore,
the progress of the reaction was monitored by recording the
time-dependent absorbance with a UV–Vis spectrophotom-
eter in a scanning range of 200–800 nm at ambient tempera-
ture. The control reactions were also performed without
both catalysts and NaBH4. The kinetics of the catalytic reac-
tion was explored by conducting all the experiments from 1
to 14 min.
In this degradation process, the CR removal efficiency
of nZVI and PEG-modified nZVI was presented as follows
(Eq. (3))]:
 
C0
Ct
Degradation efficiency ð%Þ ¼  100 (3)
C0
where C0 and Ct indicate the initial dye concentration and
final CR dye concentration left in the reaction medium at t
mint [t ¼ 2,4,6 … … 14] and the equilibrium CR dye concen-
tration during degradation was calculated using the following
equation (Eq. (4)).
4 I. SOM ET AL.
 
C0
Ce
qe ¼  V (4)
m
Herein, qe indicates the equilibrium amount of CR deg-
radation per unit mass of the catalyst (mg g
1), Ce indicates
the equilibrium concentration of CR dye solution (mg L
1),
V indicates the volume of dye solution (L) used and m indi-
cates the mass of catalyst (g) used.
The reaction kinetics was explored by following the below
equation (Eq. (5))
 
Ct
ln ¼
kt (5)
C0
where C0 and Ct imply the initial concentration and concen-
tration at time t (min) of CR solution, respectively; k is the
apparent rate constant (min
1).
TOC study was employed to measure the mineralization
of CR dyes. Estimation of TOC had been done by standard
methods using TOC analyzer (Shimadzu). The % of dye
mineralization was found using the following Eq. (6).[39]
TOC
Mineralization ¼ 1
 100 (6)
TOC0
Gas chromatography-mass spectroscopy (GC-MS)
analysis of degraded CR dye
To identify the formation of intermediates upon catalytic deg-
radation of CR, catalyst particles were removed from the
decolorized solution by centrifugation. The obtained super-
natant was extracted three times with an equal volume of
diethyl ether using a separating funnel. The desired solvent
phase was collected, dried over anhydrous Na2SO4 and dis-
solved in HPLC-grade methanol. The GC-MS (Agilent 8890;
Rtx 5 M S, Santa Clara, CA) analysis was conducted in tem-
perature programming mode with ionization voltage of 70 eV.
The initial column temperature was set to 80  C for 2 min
then increased linearly at 5  C min
1 to 300  C and held for
5 min. The GC-MS interface was kept at 290  C while the
injection port was kept at 280  C. As a carrier gas, helium was
employed and flowed at a rate of 1.0 mL per minute.
Results and discussion
Characterization of synthesized catalysts
Figure 1 depicts the XRD peaks of three synthesized cata-
lysts (a) nZVI (b) nZVI-PEG600 (c) nZVI-PEG6000 in the 2h
range of 20–80 . From Figure 1(a–c), a characteristic broad
peak at 2h of 44.8 appears, which can be ascribed to (110)
plane. This confirms the presence of a-phase of metallic
iron [Fe(0)] for all the three samples which matches well
with ICSD card no. 98-002-1567.[40] Moreover, the % rela-
tive intensity of this diffraction peak [(110) plane] is found
to be higher for the nZVI-PEG6000 sample compared to
others sample. This indicates nZVI-PEG6000 contains the
higher degree of crystallinity with larger crystallite size com-
pared to others samples (Table 1).[39] Furthermore, other
peaks (marked with asterisk) were also observed at 2h of
Figure 1. XRD pattern of (a) nZVI (b) nZVI-PEG600 (c) nZVI-PEG6000.
Table 1. Crystallite size of all the synthesized samples.
Sample ID Crystallite size (nm)
nZVI 4
nZVI-PEG600 7
nZVI-PEG6000 8
35.9 and 62.8 in case of bare nZVI and nZVI-PEG600
which represent the formation of Fe3O4 and Fe2O3, respect-
ively, on the surface of the nanoparticles. Meanwhile, these
distinct peaks were not observed in nZVI-PEG6000, suggest-
ing a small amount of the iron oxides shell.[41] Therefore, it
can be inferred that the incorporation of PEG of higher
molecular weight can effectively reduce the oxidation prob-
ability of nZVI.[42,43] Moreover, the crystallite size of the
synthesized samples has been calculated using the Scherer
equation (Equation 2) and has been listed below (Table 1).
The crystallite size of nZVI-PEG6000, i.e., 8 nm was obtained
to be highest compared to other samples.[44] The higher
crystallite size of nZVI-PEG6000 confirmed the higher degree
of crystallinity leading to the highest catalytic rate over the
other catalysts.[45] The observations from the XRD analysis
can be correlated very well with the TEM images result.
Figure 2 represents the FTIR spectra of (a) nZVI (b) nZVI-
PEG600 (c) nZVI-PEG6000 in the range of 400–4,000 cm
1. All
the spectrum shows characteristic absorption bands at 468,
682, 940, 1,314, 1,631 and 3,404 cm
1. The broad bands at
3,404 cm
1 were attributed to O–H stretching vibration of the
physisorbed water molecules. The band appearing at
1,314 cm
1 is due to the O-H bending vibration. It implies
the presence of surface hydroxyls groups on the nZVI surface.
Furthermore, the peak at 1,314 cm
1 in the FTIR spectrum of
both nZVI-PEG6000 and nZVI-PEG600 is widened compared
to bare nZVI owing to the well binding of PEG (Mw
6000)
and PEG (Mw
600) hydroxyl groups with the nZVI sur-
face.[46,47] The characteristic peaks appearing at 468, 682, 940
and 1,631 cm
1 can be assigned to the Fe-O-Fe, Fe–O stretch-
ing, Fe–O–H vibration and the antisymmetric vibration
of H2O molecules, respectively. This indicates the existence
of Fe3O4, Fe2O3 and FeOOH in PEG-modified nZVI

Figure 2. FTIR spectra of (a) nZVI (b) nZVI-PEG600 (c) nZVI-PEG6000.
samples.[48,49] FTIR result depicts the appreciable modifica-
tion of nZVI with PEG. Figure 3 represents the XPS spectra of
nZVI-PEG6000 before and after the reaction with CR dye. The
whole region XPS spectrum of nZVI-PEG6000 before the reac-
tion demonstrates that mainly elements of Fe, O, and C pre-
sent in the fresh nZVI-PEG6000 sample (Figure A12). Figure
3(a) depicts the Fe 2p XPS spectra of fresh nZVI-PEG6000.
Two narrow discrete peaks with the binding energies of 723.3
and 727.2 eV were detected which ascribed to Fe(II) and
Fe(III) (Fe2p1/2). Additionally, the peaks with 708.6 and
Figure 3. High-resolution XPS spectra of (a) Fe2p and (c) C2P for (e) O1s for fresh nZVI-PEG6000; and (b) Fe2p and (d) C2P for (f) O1s for used nZVI-PEG6000 after
Cycle 5.
JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 5
712.0 eV binding energies correspond to Fe(II) and Fe(III)
(Fe2p3/2) appeared due to the formation of a-Fe2O3.[50]
Besides a peak with low binding energy of 705.5 eV appeared
which was ascribed to Fe2p1/2 in pure Fe. In addition,
717.0 eV was attributed to the characteristic peak of
Fe(0).[51,52] Moreover, the C1s peak at 284.8 eV was ascribed
to the adventitious carbon (Figure 3(c)). The O1s XPS spec-
trum includes three shoulder peaks at 528.5, 530 and
531.2 eV, confirms the presence of structural –OH group,
physically adsorbed H2O, and C-O structural, respectively
(Figure 3(e)).[53] Herein, –OH and C-O indicates the presence
of PEG. Herein, two photoelectron peaks at 528.5 eV
appeared, which assigned to the lattice oxygen of Fe (Fe2O3),
while the other O1s peaks at around 530.3 eV indicate the
adsorbed hydroxyl group resulting from the –OH functional
group as well as bounded water molecule on the surface of
nZVI-PEG6000, respectively. In addition, similar XPS spec-
trum for nZVI-PEG600 and bare nZVI (Figure A3) was
observed. After catalytic degradation of CR using nZVI-
PEG6000 catalyst, the calculated ratio of Fe(II)/Fe(III) was
obtained to be reduced remarkably from 2.66 to 0.87, indicat-
ing that major part of Fe(II) was converted to Fe(III). The
presence of Fe(II) and Fe(III) indicates that nZVI-PEG6000
was partly oxidized to Fe2O3 and Fe3O4 during the synthesis
process. However, the Fe(0) content onto nZVI-PEG6000
remains almost same after reaction. This might be associated
due to the fact of well protection by PEG (MW ¼ 6,000) layer
around Fe(0) core.[54] This is consistent with the XRD
results.[55] The Fe2p XPS pattern of used nZVI-PEG6000 after
6 I. SOM ET AL.
five cycles revealed that the peaks of iron oxides and oxyhydr-
oxides appeared (Figure 3(b)) while peak of pure iron [Fe(0)]
disappeared. This is due to the oxidation reaction of inner
Fe(0) core to iron oxides/oxyhydroxides. Hence, a substantial
variation of the iron oxides composition was observed.
However, the newly formed oxidation products such as iron
oxides/oxyhydroxides, green rust, ferrihydrite and magnetite,
could promote the reductive transformation of contami-
nants.[56] The O1s XPS spectra could be fitted by two peaks at
binding energies of about 528.3 and 529.9 eV, respectively
(Figure 3(f)). The predominant peak at 528.3 eV was attrib-
uted to the lattice oxygen of Fe (Fe2O3), while the other O1s
peaks at around 529.9 eV was assigned to adsorbed hydroxyl
group (–OH), attached on the surface of catalyst (Fe-OHad),
lattice hydroxyl (Fe-OHlattice) and water (H2O) molecule.[57]
From Figure 3(f), it is clearly observed that the content of
bounded -OH increased during the CR degradation process,
which is in conformity with the strong Fe oxyhydroxides
XRD signals.
Information on the surface morphology and elemental
composition of the synthesized nanoparticles was obtained
using microscopic (FESEM and HRTEM) and EDS mapping
techniques, respectively. Figure 4 demonstrates the FESEM
microstructure of the as-synthesized (a) nZVI (c) nZVI-
PEG600 (e) nZVI-PEG6000 samples; the corresponding higher
magnified images are shown in Figure 4(b,d,f). All the nano-
particles were self-assembled in a chain-like pattern which is
actually an interconnected nanofiber network. The individual
nanoparticles are spherical or elliptical shaped which may be
due to the strong magnetic and surface energy of the nZVI
Figure 4. FESEM images and their corresponding magnified view of (a) and (b) nZVI; (c) and (d) nZVI-PEG600 (e) and (f) nZVI-PEG6000.
particles. The particles were aggregated due to the higher sur-
face charge of the smaller particles. However, upon modifica-
tion of nZVI with PEG, the agglomerating tendency of
nanoparticles is somehow diminished. Hence, this forms a
sheet-like structure which is revealed from (Figure 4(d,f)). It
is interesting to note that the mesopore is clearly visible
(Figure 4(f)) suggesting better catalytic activity.
Figure 5 represents the TEM image of (a) nZVI (c)
nZVI-PEG600 (e) nZVI-PEG6000; the corresponding higher
magnified images are illustrated in Figure 5(b,d,f). All the
nanoparticles have similar chain-like/branched structures.
Herein, the spherical shape of individual particles is promin-
ent due to the prevalence of magnetic effects between the
small particles. A outer shell around Fe(0) nanoparticles was
appeared to be clearly visible (Figure 5(d,f)), which confirms
the successful modification of nZVI using PEG. From the
TEM image (Figure 5(b)) of nZVI-PEG6000, the particle size
was found to be about 20–50 nm. In addition, in case of
nZVI-PEG600 and nZVI-PEG6000, 2–5 nm thickness of PEG
layer was calculated. Herein, the fringe images (Figure A4)
show d spacing value of around 0.25 nm for nZVI-PEG6000
corresponding to the lattice plane of (110) of the zero valent
iron [Fe(0)] phase. The absence of discernible lattice fringe
in TEM images suggests the amorphous nature of nZVI and
nZVI-PEG600. However, the concentric rings of the SAED
pattern for nZVI-PEG6000 indicates slight polycrystalline
nature of nZVI-PEG6000 [58] and the identified planes well
supports the XRD results. The Energy-dispersive X- Ray
(EDAX) spectra of all the synthesized samples demonstrate
that only Fe and O present in their atomic ratio (the C and

Figure 5. TEM micrographs and their corresponding magnified view of (a) and (b) nZVI; (c) and (d) nZVI-PEG600 (e) and (f) nZVI-PEG6000.
Cu elements appeared from the grid) (Figure A5). The per-
centage of Fe and O in nZVI-PEG6000 sample was obtained
to be highest and lowest, respectively, compared to the other
samples which indicate that PEG of higher molecular weight
can protect and stabilize the nZVI core strongly. The aver-
age atomic percentage ratio of Fe and O is found to be
9.131:1 for nZVI-PEG6000 .
Figure 6 depicts the nitrogen adsorption–desorption iso-
therms of the synthesized samples. As shown in Figure 6, the
isotherms of nZVI-PEG600 and nZVI-PEG6000 can be attrib-
uted to type IV, while that of nZVI to type II according to the
IUPAC classification. Therefore, the mesoporosity in these
sample can be considered. On the other hand, the
Figure 6. N2 adsorption–desorption isotherms of (a) nZVI (b) nZVI-PEG600 and
(c) nZVI-PEG6000.
JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 7
microporous nature was observed in nZVI surface. All the
isotherm exhibits H3 type hysteresis loop indicating the pres-
ence of asymmetric, interconnected slit-like pores in the sam-
ples.[59] The textural properties (surface area, pore volume
and average pore diameter) of the synthesized samples have
been presented in Table A2. It can be seen that nZVI-PEG6000
possesses highest surface area (143.1635 m2g
1) and pore vol-
ume (0.1056 cm3 g
1). In addition, nZVI-PEG6000 has the
smallest average pore radius of 63.299 Å. Higher specific area
is beneficial for enhanced catalytic activity.
Catalytic activity of synthesized nanoparticles
The catalytic activities of synthesized nanoparticles were
examined by exploring the reductive degradation of CR, a
recalcitrant anionic dye. Figure A6(a–c) illustrates the UV
absorption spectra of the CR degradation in presence of
NaBH4 by nZVI-PEG6000, nZVI-PEG600 and nZVI, respect-
ively. As can be seen from the spectra (Figure A6), the inten-
sity of strong characteristic band of CR at kmax ¼ 497 nm was
found to be decreased gradually and almost vanished within
14 min reaction time. Herein, the absorption band at 343 nm
is attributed to the p–p transition of the aromatic ring. In
addition, the band appeared at 497 nm can be ascribed to the
n–p transition of the lone pair which is present in the N
atom of the chromophoric –N ¼ N– azo moiety.[60] Hence,
the decrease in the intensity at 497 nm indicates the cleavage
of –N ¼ N– bond. Before the cleavage of –N ¼ N– azo bond,
an electron-deficient reaction center, i.e., carbon ion is
formed within CR molecule. In this case, CR dye acts as an
electrophilic center. Hence, this electrophilic center is prone
to be attacked by a nucleophile, i.e., BH4
ion (electron
8 I. SOM ET AL.
donor) present in aqueous solution. So, initially the nucleo-
phile, BH4
can donate electrons to all the catalysts; next the
electrophile CR can receive electrons from the catalysts.[61] In
this case, all the prepared catalyst behaves as an electron relay
for CR reduction in a NaBH4 solution. In this way facile CR
dye was fragmented into small molecules. The CR removal
occurred at faster rate using nZVI-PEG6000 than both nZVI-
PEG600 and bare nZVI. Figure 7 represents the % removal of
CR using all the synthesized nano catalysts in presence of
NaBH4. It exhibits that the % of dye removal efficiency for
nZVI, nZVI-PEG600 and nZVI-PEG6000 was obtained to be
47.9%, 89.6% and 99.2%, respectively (Figure 7(a)). The max-
imum removal efficiency using nZVI-PEG6000 was achieved
due to its highest BET surface area, maximum pore volume
and pore diameter (Table A2). Herein, the Langmuir–
Hinshelwood pseudo-1st-order kinetics model was substan-
tially employed to determine the reaction rates of heteroge-
neous catalytic degradation. In accordance with this model,
the reaction rate is directly proportional to the surface cover-
age of the dye molecules on the catalytic surface.
The plot of ln (Ct/C0) vs. reaction time (Figure 7(b))
shows a linear diagram, from its slope value the rate con-
stant of the degradation process was determined. The bar
diagram reveals the obtained rate constant value for all the
prepared catalysts (Figure 7(c)). According to Equation (5),
the calculated apparent rate constant (kapp) for nZVI, nZVI-
PEG600 and nZVI-PEG6000 was obtained to be 5.1  10
2,
11.4  10
2 and 17.3  10
2 min
1, respectively. A hike in
rate constant value was observed from bare nZVI to nZVI-
PEG6000 which is owing to the excellent stabilization of
Fe(0) core by PEG (M.W. ¼ 6,000) layer in reaction
medium. Henceforth, the reductive degradation of CR dye
using all the synthesized catalysts was fitted with the
pseudo-1st-order kinetics perfectly.[62] Moreover, the
obtained maximum removal efficiency and rate constant
value for nZVI-PEG6000 can be explicated on the surface
charges of synthesized samples. The zeta potential values for
Figure 7. Plot of (a) removal efficiency, (b) ln (Ct/C0) vs. time and (c) bar plot depicting rate constant for reductive degradation of Congo red (CR) dye for all the
synthesized catalysts.
nZVI, nZVI-PEG600 and nZVI-PEG6000 were obtained to be
þ27.2, 28.0 and 30.3 mV, respectively (Figure A7). This
result implies that the adsorption of anionic dye (i.e., CR)
onto the positively charged catalytic surface occurred in a
facile manner through the electrostatic interaction. Thus,
it can be inferred that the textural properties as well as
positive surface charge play crucial role for the effective CR
degradation. Therefore, the highest catalytic efficiency of
nZVI-PEG6000 for CR degradation is explicated based on its
higher positive surface charge, maximum BET surface area
and highest pore volume. Furthermore, two different set of
control experiment was performed for investigating the syn-
ergistic effect of both nZVI-PEG6000 and NaBH4 during CR
degradation: (i) in the presence of only NaBH4 (ii) in the
presence of only catalyst (nZVI-PEG6000). Figure A8(a) illus-
trates the degradation of CR by only NaBH4 without nZVI-
PEG6000 catalyst for a time period of 14 min. In this case,
very small decreasing trend of the absorption maximum
(overlapped nature of UV–Vis spectra shown by inset
image) suggests that the degradation of CR occurred in
extremely slow rate and sufficient degradation was not
achieved. Actually, electrons transfer process from donor
BH4
to -N ¼ N- bond of acceptor CR, via conveyer belt,
i.e., catalyst become hamper.[63] Hence, very small %
removal efficiency, i.e., 7.08 with apparent rate constant
value of 0.21  10
2 min
1 was achieved (Figure A9(a)).
Similarly for the second control experiment in presence of
only nZVI-PEG6000 (Figure A9(b)), no efficient CR degrad-
ation was achieved upto 14 min of reaction time. In this
case, % removal efficiency of 6.07 with rate constant value
of 0.24  10
2 min
1 was obtained. Herein, facile electron
transfer process is hindered due to the absence of any elec-
tron donor, i.e., BH4
ion. Only some portions of CR dye
were adsorbed onto the surface of catalysts, leads to low %
of CR removal efficiency. These control experiments indicate
that the synergetic effect of the catalyst and NaBH4 was vital
for the efficient removal of CR dye.[64]

Figure 8. Plot of (A) degradation efficiency, (B) ln (Ct/C0) vs. time for reductive degradation of Congo red (CR) dye by using nZVI-PEG6000 under different catalyst
dosage.
Effect of different reaction parameter
Effect of catalyst dosage
Effect of catalyst dosage on CR dye degradation was studied
by keeping the other reaction parameter constant (Figure 8).
It can be inferred that dye degradation rate enhanced from
0.059 to 0.175 min
1 with increasing the catalyst dosage
from 0.1 to 0.2 gL
1, but dropped with excessive catalyst
loading (0.124 min
1 at 0.4 gL
1 catalyst dosage). With the
increase in the catalyst dosage, the increase in the degrad-
ation rate could be attributed to the increase in catalytic
sites and reactive surface. As a result, available actives sites
become optimal to accommodate all the CR molecules on
the catalyst surface as well as feasible electron transfer pro-
cess from BH4
ion to CR molecule via catalytic center
enhanced.[65] However, in the presence of excessive catalyst
dosages, the active sites on catalyst are reduced, because of
the production of aggregates and consequently self-binding
of catalyst particles.[66] Figure 8(a) shows the plot of % CR
removal efficiency vs. time at different catalyst dosage. The
highest % CR removal efficiency of 99.2% was achieved at
0.2 gL
1 catalyst dosage. Therefore, the optimum catalyst
dosage is desirable for efficient catalytic degradation of CR.
Effect of initial dye concentration
Effect of initial dye concentration on CR dye degradation rate
was determined by keeping other reaction parameters con-
stant (Figure 9). Findings showed that with an increase in the
dye concentration from 1  10
5 to 2  10
5 molL
1, CR
degradation rate increases from 0.081 to 0.175 min
1.
Furthermore, it gradually decreased at higher concentration
of CR dye (4  10
5 molL
1). The initial rise of reaction rate
can be explained by the easy accessibility of the active sites on
the catalytic surface which can accommodate all the dye mole-
cules, feasibly migrated from solution to the surface.
Meanwhile, due to the high concentration of dye molecule,
the fixed dose of catalyst can degrade only the limited quan-
tity of dye molecules. Hence, the remaining dye molecules
stay in the bulk reaction medium before being migrated to the
surface till the former attached dye molecules are degraded.
JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 9
Thus, the active sites of the catalyst become depleted owing to
such stepwise dye degradation process dramatically. As a
result, dye degradation rate decreases. Besides, a plausible
competition takes place between the reaction products or the
produced intermediates and the unreacted dye molecules to
be attached on the catalytic surface significantly. Therefore,
the catalyst surface becomes poisoned due to such inhibitive
effect of reaction products or the intermediates.[67,68] The plot
of % CR removal efficiency vs. time under different dye con-
centration is also represented in Figure 9(a). The highest %
CR removal efficiency of 99.2% was achieved at 2  10
5 mol
L
1optimum CR dye concentration.
Effect of NaBH4 concentration
The concentration of NaBH4 has a remarkable influence on
the effective catalytic reduction rate of CR. Initially, upon
increasing the concentration of NaBH4 from 0.05 to
0.1 molL
1 the catalytic reduction rate of CR increased from
0.045 to 0.0719 min
1 significantly (Figure 10). Additionally,
the removal efficiency was also enhanced owing to the rapid
electron transfer process. On the other hand, excessive
NaBH4 concentration (0.2 molL
1) leads to the CR reduc-
tion rate unchanged. This may be attributed upon increasing
the NaBH4 concentration after certain limit no additional
electron transfer process occurs as the amount of both dye
molecule and catalyst is fixed in reaction media.[69] With
increasing the NaBH4 concentration additional electron
transfer from BH4
to dye molecule via catalyst do not
occur. Hence, after certain concentration of NaBH4, the CR
dye removal rate remains unchanged.
Influence of electrolytes
Electrolytes present in reaction media play a crucial role
upon effective degradation of dye by catalysts. So, we inves-
tigated the impacts of electrolytes on CR degradation rate by
nZVI-PEG6000 using NaBH4. Figure 11 represents the vari-
ation of % removal efficiency with the reaction time by the
addition of different salts in reaction mixture. The catalytic
properties of nZVI-PEG6000 depend drastically on the nature
10 I. SOM ET AL.
Figure 9. Plot of (a) removal efficiency, (B) ln (Ct/C0) vs. time for reductive degradation of Congo red (CR) using nZVI-PEG6000 under different dye concentration.
Figure 10. Plot of (a) removal efficiency, (b) ln (Ct/C0) vs. time for reductive degradation of Congo red (CR) dye by using nZVI-PEG6000 under different NaBH4
concentration.
Figure 11. Influence of electrolyte on the decolorization of CR by nZVI-PEG6000
catalyst.
of some electrolytes. Herein, 0.05 mol L
1 sodium nitrate
(NaNO3), sodium sulfate (Na2SO4) and sodium phosphate
(Na3PO4) were used as electrolytes. The degree of CR deg-
radation followed the decreasing order: NaNO3 > Na2SO4
> Na3PO4. Therefore, the reductive degradation rate of CR
dye increases in presence of NaNO3 and Na2SO4 (Figure
11). However, Na3PO4 decreased the catalytic reduction rate.
This phenomenon can be attributed on basis of facilitated
charge migration. NaNO3 and Na2SO4 can accelerate the
electron migration from NaBH4 to catalytic surface. As a
result, CR degradation rate increases. On the contrary,
Na3PO4 adsorbed preferentially onto the surface of nZVI-
PEG6000 catalyst. The decrease in the degradation of CR in
the presence of phosphate ions might be attributed to com-
petitive adsorption between PO43
and anionic CR dye on
the surface of the catalyst.[70] This phenomenon leads to the
blockage of active sites of catalysts.[71] Thus, the adsorption
of CR dye molecules was inhibited, as a result slow degrad-
ation rate was achieved.
Total organic carbon (TOC) analysis
Although complete decolorization of CR dye occurs within
14 min of reaction, it does not signify the total mineraliza-
tion of CR dye into CO2 and H2O. Hence, we have per-
formed the TOC analysis which is a crucial experiment to
confirm the total mineralization of CR into CO2 and
H2O.[72] According to Figure 12, % TOC removal increases
with increasing the reaction time, suggesting the efficient
mineralization of CR dye. Although, the UV–vis spectra

Figure 12. Plot of % TOC removal vs. time.
reveals 99% decolouration after 14 min, yet the TOC ana-
lysis demonstrates that 79% of maximum TOC removal
efficiency was achieved after 45 min (Figure 12). Since CR
molecules were decomposed to several intermediates and
by-products during degradation process, a longer contact
time was required for sufficient TOC degradation compared
to the decolorization process.[73]
GC–MS analysis for the Congo red degradation
In our study, GC–MS was employed for the identification of
the intermediate products produced during CR degradation
in presence of NaBH4. Figures A10 and A11 represent the
total chromatogram and the mass spectra of plausible
degraded products, respectively. Based on the m/z value, the
structures of the identified products were determined. GC–
MS results shows the appearance of 3,4-diaminonaphthalene-
1-sulfonic acid (m/z ¼ 239; Figure A11(a)) and 1,10 -biphenyl-
4,40 -diamine (m/z ¼ 185; Figure A11(b)), which forms due to
the cleavage of azo bond (–N ¼ N). Afterwards, the deamin-
ation process leads to the formation of 1,10 -biphenyl
(m/z ¼ 154; Figure A11(c)) and 4-aminonaphthalene-1-sul-
fonic acid (m/z ¼ 223). However, removal of both –NH2 and
–SO3H group from 3,4-diaminonaphthalene-1-sulfonic acid
results the formation of naphthalene molecule (m/z ¼ 128;
Figure A11(d)). After several steps, the aromatic ring ruptur-
ing or ring cleavage produces low molecular weight inter-
mediate compounds such as succinic acid (m/z ¼ 119; Figure
A11(g)), malonic acid (m/z ¼ 105; Figure A11(g)), etc. The
succinic acid may be decomposed forming acrylic acid
(m/z ¼ 73; Figure A11(h)). Finally, succinic acid, malonic acid
and other organic acid were mineralized to carbon-di-oxide
and water in reaction medium.
Elucidation of plausible mechanistic pathway of CR
degradation
Based on the m/z value obtained from the GCMS analysis
degraded products, a plausible mechanistic pathway of CR
JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 11
degradation has been illustrated in Scheme 2. At first signifi-
cant adsorption of CR molecule on the surface of synthe-
sized nZVI-PEG6000 occur. Then, an electron-deficient
reaction center (carbocation ion) is generated in the catalytic
cavity of CR molecule. This carbocation ion is highly prone
to react with nucleophile, i.e., BH4- ion which transfer elec-
trons to nano catalyst. Later, this electrons attacked the
carbocation ion, which leads to the cleavage of electronically
unstable azo bond. The color of CR is due to the presence
of azo bond along with chromophores.[74] Thus, cleavage of
azo bond causes its decolorization gradually. Later, the vari-
ous steps including demination (–NH2), desulphonation
(–SO3H) and ring cleavage or rupturing process leads to the
formation of several low molecular weight intermediate
compounds. The obtained low molecular weight compounds
(dicarboxylic acid, other organic acid) are finally mineralized
to CO2 and H2O.
The reductive degradation of two dyes mixture
The degradation of two anionic dyes, i.e., CR and MO mix-
ture was employed to establish the potentiality of the syn-
thesized nZVI-PEG6000 catalyst in presence of NaBH4. The
progress of the reaction was monitored by UV–Visible spec-
tra (Figure 13). The distinctive UV–Vis peak at kmax ¼ 498
and 464 nm for CR and MO dye, respectively, was vanished
upon adding NaBH4 to the mixture of dyes. A new peak at
about kmax ¼ 477 nm appeared upon mixing of CR and
MO. The intensity of this distinct peak gradually decreased
with increasing the reaction time. The peaks at 477 nm were
completely vanished after 14 min of the reaction time.
Hence, the reaction mixture was totally decolorized (Figure
13). Figure A15 depicts the UV–Vis spectra of the individual
dye (CR and MO). These results infer that the synthesized
nZVI-PEG6000 can act as a promising catalyst for effective
degradation of mixture of multiple organic dyes.
Reusability studies
The stability and reusability of a catalyst play crucial role in
a catalytic degradation process. The reusability of nZVI-
PEG6000 catalyst was tested in CR dye degradation reaction
for five successive runs. The catalyst after reaction was sepa-
rated via magnetic separation from the reaction media using
a horshoe magnet. Then, the recovered catalysts were
washed with distilled water and ethanol three times and
dried in vacuum for the next cycle of usage. Figure A12
illustrates the bar plot of the % removal efficiency vs. num-
ber of runs. It is clear from Figure A12 that the catalyst was
almost stable up to four cycles. Thus, nZVI-PEG6000 can be
considered as a highly stable nano catalyst for efficient deg-
radation of dye. XRD and XPS characterization technique
was employed for investigating the changes of nZVI-
PEG6000 obtained after catalysis (Figures A13 and A14).
Herein, XRD analysis revealed that diffraction peak at 2h
value of 35.2 with low intensity corresponds to a-Fe2O3
(Figure A13). It indicates that some portions of Fe(0) core
was oxidized during reaction. Furthermore, XPS analysis
12 I. SOM ET AL.

Scheme 2. Plausible catalytic mechanism for reductive degradation of Congo red by nZVI-PEG6000.

Figure 13. UV–Vis spectra of reductive-degradation of the dye mixture contain-
ing Congo red and methyl orange at various time intervals using nZVI-PEG6000.
demonstrates that only the characteristic peaks attributed to
Fe(II) and Fe(III) at 709.2 and 711.4 eV, respectively,
appeared. Again, the characteristic peak of Fe (0) (Figure
A14), was disappeared after the reaction. It may be due to
the oxidation of Fe(0) moiety to Fe(II) and Fe(III). This
result indicates that Fe(0) core within nZVI-PEG6000 partici-
pates in the degradation reaction of CR.
Conclusions
In conclusion, we demonstrated a facile chemical reduction
method for synthesis of bare nZVI and PEG (containing
various molecular weight) modified nZVI at room tempera-
ture. XRD and FTIR analysis confirmed the formation of
PEG-modified nZVI. FESEM and TEM study revealed the
formation of spherical-shaped particles of different size.
From the TEM images, the organized and uniform PEG
layer around Fe(0) core indicates the successful modification
of nZVI using PEG. A comparative catalytic activities of as-
prepared nanoparticles were investigated by the reduction of
hazardous CR dye with NaBH4. Moreover, the as-synthe-
sized nZVI-PEG6000 showed excellent catalytic activity
(Removal efficiency of 99.2% in 14 min) over the other cata-
lyst. The textural properties as well as the positive surface
charge are crucial for the efficient catalytic degradation of
CR dye. From the kinetic studies, it can be concluded that
CR degradation process follows pseudo 1st-order kinetics.
Investigation on the influence of different reaction param-
eter results 0.2 gL
1 catalyst dosage, 2  10
5 molL
1 dye
concentration and 0.1 molL
1 NaBH4 concentration as opti-
mum reaction parameter. The finding of %TOC removal
experiment confirms the complete mineralization of CR
after reaction. The degradation of CR to several intermedi-
ates products occurred using the nZVI-PEG6000 catalyst as
confirmed by GCMS. Furthermore, the complete degrad-
ation of CR and MO dye mixture using nZVI-PEG6000 as
catalyst was achieved within 14 min. Additionally, it was
shown that the nZVI-PEG6000 nanocatalyst is a highly effi-
cient and recyclable catalyst for related reactions that can be
JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 13
recovered and reutilized several times without significant
loss of its catalytic activity. Hence, we anticipate that by uti-
lizing PEG materials in nanoparticle, the modified nanoma-
terial can be a better candidate with improved catalytic
properties. In addition, this strategy could be an effective
method for the future modification of catalyst.
Acknowledgments
We would like to acknowledge Science & Technology and
Biotechnology Department, Govt. of West Bengal (Project Memo No.
47 (Sanc.)/ST/P/S & T/15G17/2018 dt. 30.01.2019) and National
Institute of Technology Durgapur for providing infrastructure and
financial support to accomplish the work fruitfully. Department of
Science and Technology under the SERB (N-PDF) sponsored project
(No. PDF/2017/000390), Government of India was also acknowledged.
Conflicts of interest
The authors declare that there are no conflicts to declare.
Author’s contributions
Main manuscript writing: Ipsita Som, Perceived and designed the
experiments: Ipsita Som and Mouni Roy, Execution of experiments:
Ipsita Som Data collection and analysis: Ipsita Som Data interpretation:
Ipsita Som and Mouni Roy, Guidance and funding: Rajnarayan Saha.
All authors reviewed the manuscript carefully.
ORCID
Ipsita Som http://orcid.org/0000-0002-4788-2851
Rajnarayan Saha http://orcid.org/0000-0001-6167-2271
Data availability statement
The authors confirm that the data supporting the findings of this study
are available within the article and its Appendix.
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Appendix
Figure A1. Structures of (a) CR and (b) MO dye generated using ChemDraw.
Figure A2. Magnetic separation of synthesized nanoparticles from reaction media.
Cotton Textiles for Catalytic Degradation of Congo Red. J.
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 JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 17

Figure A3. High resolution XPS spectra of (a) Fe2p and (c) C2P for (e) O1s for bare nZVI- and (b) Fe2p and (d) C2P for (f) O1s for nZVI-PEG600.
18 I. SOM ET AL.

Figure A4. The HR-TEM images (a, c, e); selected area electron diffraction (SAED) pattern (b, d, f) of nZVI, nZVI-PEG600 and nZVI-PEG6000 respectively.
 JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 19

Figure A5. Energy dispersive X-Ray spectra (EDS) of prepared (a) nZVI (b) nZVI-PEG600 and (c) nZVI-PEG6000.

Figure A6. Successive UV-vis absorption spectra with time for the catalytic degradation of Congo Red (CR) dye at 25  C for (a) nZVI-PEG6000 (b) nZVI-PEG600 and
(c) nZVI.
20 I. SOM ET AL.

Figure A7. Zeta potential of (a) nZVI (b) nZVI-PEG600 and (c) nZVI-PEG6000.

Figure A8. Successive UV-vis absorption spectra with time for degradation of Congo Red (CR) (blank tests) under different conditions: (a) in the presence of NaBH4
only without any catalyst and (b) in the presence of nZVI-PEG6000 catalyst only without NaBH4.

Figure A9. Plot of (A) degradation efficiency, (B) ln(Ct/Co) vs. time of blank tests under different conditions for degradation of Congo Red (CR) dye: (a) in the pres-
ence of NaBH4 only without any catalyst and (b) in the presence of nZVI-PEG6000 catalyst only without NaBH4.
 JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 21

Figure A10. Full Chromatogram of degraded Congo Red dye.

Figure A11. Mass spectra correspond to the molar masses of the Congo Red degraded various intermediate products.
22 I. SOM ET AL.

Figure A12. Reusability study of nZVI-PEG6000 catalyst upto 5th run.

Figure A13. XRD pattern of all used catalyst after 5th cycle reaction.

Figure A14. XPS survey spectra of fresh and used nZVI-PEG6000.

 JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 23

Figure A15. UV-Vis spectra of (a) Congo Red and (b) Methyl Orange dye.

Table A1. The properties of CR.

C.I. name Molecular Weight/g.mol-1 λmax/nm Molecular formula
Congo Red 696.66 498 C32H22N6Na2O6S2
Chemical Structure

Table A2. The textural properties of three catalysts.

Surface area Pore Volume Pore diameter
Sample Name (SBET, m2g
1) (Vp) cm3 g
1 (Dp) Å
nZVI 29.3942 0.044420 108.0459
nZVI-PEG600 63.6574 0.083669 78.8331
nZVI/PEG6000 143.1635 0.1056 63.299
24 I. SOM ET AL.
Table A3. Comparison with existing literature in catalytic degradation of organic pollutants by zero valent iron nanoparticle based nanomaterials.
Nanomaterial as
Sr. No. catalyst
1 Bare nano zero valent iron
particles(BNZVI),
hydroxyethyl cellulose
modified (ENZVI) and
hydroxypropylmethyl
cellulosemodified (PNZVI)
2 Oak leaves extracted zero
valent iron nanoparticle
(OAK-nZVI)
3 Zero valent iron combined
with multiwalled carbon
nanotube (ZVI-MWCNTs)
4 Rectorite-supported nZVI
(nZVI/R)
5 Nanoscale zero-valent
iron (nZVI)
6 Silica gel supported
nZVI(Fe0-Si) & starch
supported nZVI
composites (Fe0-St)
7 Kaolin supported nanoscale
zero-valent iron (K-nZVI)
9 Bare nZVI, Polyethylene
glycol (M.W.- 600)
modified nZVI (nZVI-
PEG600) Polyethylene
glycol
(M.W.- 6000) modified
nZVI (nZVI-PEG6000)
Target pollutant Reaction condition % Removal efficiency Reference
Orange II , Methyl orange, Initial dye conc: 100 mgL-1 Orange II: 76.4% by BNZVI, [1]
Methyl blue, Methylene Catalyst dosage: 0.7 g L-1 82.5% by ENZVI, 88% by
blue Reaction time: 60 min PNZVI
Methyl orange: 51.9% by
BNZVI, 62.5% by ENZVI,
66.4% by PNZVI
Methyl blue: 79.6% by
BNZVI, 93.1% by ENZVI,
94.1% by PNZVI
Methylene blue: 67.7%
by BNZVI, 74% by ENZVI,
80.9% by PNZVI
Magenta dye Initial dye conc.:180 mgL-1 94% [2]
Catalyst dosage:
60 mgL-1 , H2O2 conc.:
11mM at pH 2
Reaction time : 60 min
Reactive Red 198 Initial dye conc.:100 mgL-1, 99.16% [3]
ZVI dosage:
5000 mgL-1 , MWCNTs
dose ¼ 600 mgL
1 at
pH 3
Reaction time : 100 min
Methyl orange & Initial dye conc.:100 mgL-1, Methyl orange – 93% [4]
Metronidazole ZVI dosage: Metronidazole-97%
0.5 gL-1 , at pH 9
Reaction time : 20 min
Norfloxacin nZVI dosage: 95% [5]
100 mgL-1 ,
H2O2 conc.- 20 mmolL-1
at pH 4
Reaction time : 40 min
Acid Blue-25 Initial dye conc.: 50 ppm, 99.8 % for Fe0-Si [6]
Catalyst dosage: 96.5 %for Fe0-St .
2 gL-1 , at pH 1
Reaction time : 6 min
Direct Black G Initial dye conc.: 100 mgL-1, 97.4% [7]
Catalyst dosage:
0.6 gL-1 , at pH 9.49
Reaction time : 30 min
Congo Red Initial dye conc.: 2X10-5 47.9%, 89.6% and Our work
molL-1, Catalyst dosage: 99.2%
0.2 gL-1 ,
Reaction time : 14 min