Microporous and Mesoporous Materials 267 (2018) 68–79

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Microporous and Mesoporous Materials

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

Polyaniline/FeZSM-5 composites – Synthesis, characterization and their T

high catalytic activity for the oxidative degradation of herbicide glyphosate
Maja Milojević-Rakića,∗, Danica Bajuk-Bogdanovića, Bojana Nedić Vasiljevića, Aleksandra Rakića,
Sandra Škrivanjb, Ljubiša Ignjatovića, Vera Dondura, Slavko Mentusa, Gordana Ćirić-Marjanovića
a
Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11158, Belgrade, Serbia
b
Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, 11158, Belgrade, Serbia

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

Keywords: Semiconducting composites of nanostructured and granular polyaniline (PANI) with FeZSM-5 zeolite were
Polyaniline synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in water, without added
Zeolite acid and in an aqueous H2SO4 solution, in the presence of FeZSM-5, by using initial weight ratios aniline/FeZSM-
Composites 5 of 1/1 and 1/5. These novel composite materials, in their as-synthesized (protonated) and deprotonated forms,
Glyphosate
were characterized by elemental, thermogravimetric and differential thermal analysis, scanning electron mi-
Oxidative degradation
croscopy, FTIR and Raman spectroscopy, X-ray powder diffraction and conductivity measurements. The catalytic
activity of the PANI/FeZSM-5 composites towards the oxidation of herbicide glyphosate with hydrogen peroxide
has been investigated. A significant improvement of the catalytic activity of PANI/FeZSM-5 composites com-
pared to that of pure PANI and FeZSM-5 was observed, manifested by the almost one order of magnitude more
efficient oxidative degradation of glyphosate with hydrogen peroxide. The maximum of oxidized/decomposed
amount of glyphosate was achieved in the presence of PANI/FeZSM-5 composite synthesized using an initial
aniline/FeZSM-5 = 1/5 wt ratio. It has been shown that the method of synthesis and interactions between PANI
and zeolite in this complex composite system, leading to more efficient electron transfer and hydrogen peroxide
decomposition, are crucial for the catalytic properties of tested PANI/FeZSM-5 materials. It is shown that new
PANI/FeZSM-5 composites present advanced catalyst materials for enhanced green catalytic degradation of
pesticide/herbicide pollutants in environmental remediation systems.

1. Introduction PANIs synthesized within the zeolite channel system [2–4,6,7,12,22] or at

There is a growing interest in the development of conductive poly-
mers/zeolites (nano)composites in order to obtain new materials with
synergistic or complementary properties for various applications [1]. A
special attention was paid to the synthesis and characterization of poly-
aniline (PANI) composites with zeolites [2–32]. The preparation of PANI/
zeolite composites was accomplished by the oxidation of aniline within the
zeolite (Y, HY, HZ, HS, MCM-41, ZSM-5, β-zeolite) channel system
[2–4,6,7,12,22], by chemical [5,8,9,15–19,23–27,29–32], electrochemical
[5,28], emulsion [10], and enzymatic [20] oxidative polymerizations of
aniline in the presence of various zeolites (e.g., MCM-41, 13X, β-zeolite,
FUYB, Y, HY, NaY, ZSM-5, amine-functionalized ZSM-5, clinoptilolite, and
erionite), by dry mixing of PANI powder with zeolites such as Y, HY, 13X,
MCM-41, and LTA [13,14,27], and by the addition of some zeolites (e.g.,
Zenith-N, LTN) to the PANI solution [11,21]. Plenty of experimental
spectroscopic evidences (FTIR, UV–Vis, Raman, EPR, etc.) indicated that
the zeolite surface [5,8–10,15–20,23–32] exist in the conducting emer-
aldine salt form, which depending on synthetic conditions and isolation
procedures contains localized/delocalized polarons and bipolarons in
various proportions (Scheme 1). The applicability of PANI composites with
zeolites for solid state pH electrodes [17], gas (CO, CO2, NO2, NH3, H2O,
alkylamines) sensors [13,14,19,27,31], sensors for epinephrine [33],
paracetamol [33], folic acid [33], lindane [34], acetylcholine [30], orga-
nophosphates [30], hydrazine [35], and phenylhydrazine [35], as well as
the usability of PANI/zeolite composites as antiferromagnetic materials
[9], cathodes in a primary cell (battery) [11,21], curing agents for epoxy
resin [10], corrosion inhibitors [24,28], membranes [26], catalysts [36],
components of electrorheological fluids [37], sorbents for multiresidue
analysis of pesticides [32], and adsorbents [38], was also thoroughly in-
vestigated.
PANI/zeolite composites were proved to be efficient adsorbents for
environmental pollutants, e.g., herbicide glyphosate [N-(phosphonomethyl)

∗
Corresponding author.
E-mail address: maja@ffh.bg.ac.rs (M. Milojević-Rakić).

https://doi.org/10.1016/j.micromeso.2018.03.019
Received 2 November 2017; Received in revised form 26 February 2018; Accepted 13 March 2018
Available online 15 March 2018
1387-1811/ © 2018 Elsevier Inc. All rights reserved.
M. Milojević-Rakić et al.
Scheme 1. Bipolaron and polaron form of PANI emeraldine salt. An anion (counter-ion,
e.g. hydrogensulfate) is denoted by A–.
glycine] which is toxic to aquatic life with long lasting effects [39], and Cr
(VI) compounds (chromates, dichromates, etc.) [29] which show both the
acute and chronic toxicity to aquatic organisms [39]. The potential appli-
cation of PANI/zeolite composites for efficient removal of herbicide and
other pesticide pollutants from wastewaters looks especially promising and
interesting. The efficient removal of pesticide pollutants, which accumulate
in the environment because more than 99.9% of pesticides actually do not
reach the intended target pests [40], represents a significant scientific
challenge over the past three decades. One of the current problems is the
unloading and cleaning of pesticide/herbicide containers which lead to the
contamination of ground and underground waters [41]. Wastewaters
usually contain rather high quantities of pesticide/herbicide molecules
(order of magnitude being mgL−1) while in water flows these concentra-
tions are in the order of μgL−1. In the case of the well-known post-emer-
gence, non-selective, systemic herbicide glyphosate, which is extensively
implemented in agricultural and urban environments [42], it was revealed
that glyphosate quantities detected in ground water in certain cases were
somewhat above its maximum contaminant level of 700 μgL−1 [43] ac-
cording to the ecological U.S. standards. It should be noted that glyphosate
quantities detected in ground water were 3–4 orders of magnitude higher
than its maximum contaminant level of 0.1 μgL−1 according to the much
more rigorous ecological EU regulation [44]. Therefore, a development of
the efficient remediation techniques for the removal of glyphosate became
an emerging task for the scientific community in recent years. An efficient
adsorption technique for the glyphosate removal from aqueous solutions, by
using the nanostructured and granular PANIs and their composites with
zeolite HZSM-5 as adsorbents, has been developed by our research group
[25]. However, it should be noted that it is generally expected that only
combination of adsorption techniques and chemical methods could give
satisfactory results in pesticide/herbicide removal from wastewaters with
different levels of contamination, because adsorption techniques for pesti-
cide/herbicide removal require additional step of the regeneration/recovery
or destruction of pollutant-containing adsorbents, while chemical methods
often result in incomplete removal or unwanted side products [45].
Advanced oxidation processes for pesticide/herbicide removal from
wastewaters often include Fenton reactions in systems for catalytical
decomposition of H2O2 which produce hydroxyl radicals in the pre-
sence of ferrous ions or hydroperoxyl radicals in the presence of ferric
ions. This reaction could be employed for oxidation and removal of
various organic compounds [46]. Amongst heterogeneous Fenton cat-
alysts, special attention was given to zeolites with iron present as fra-
mework and extra-framework ions [47,48].
Based on (i) the fact that chemical catalytic processes comprising
hydrogen peroxide as oxidant were successfully utilized in the gly-
phosate decomposition/removal [41,49], (ii) the finding that Fe-doped-
zeolites (FeZSM-5, etc.) were successfully used as catalysts in the oxi-
dative degradation of some organic pollutants with hydrogen peroxide
(H2O2) [47,50], and (iii) our study showing excellent adsorption
properties of PANI and PANI/HZSM-5 composites towards glyphosate
[25], here we present the investigation of catalytic properties of FeZSM-
5 zeolite, PANI, and novel PANI/FeZSM-5 composites in the oxidative
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Microporous and Mesoporous Materials 267 (2018) 68–79
degradation of pesticide glyphosate with hydrogen peroxide.
2. Experimental
2.1. Materials
Aniline (p.a., Centrohem, Serbia) was distilled under reduced
pressure and stored in argon, prior to use. Sulfuric acid (H2SO4) 96%
(p.a., Centrohem, Serbia), ammonium peroxydisulfate (APS) (p.a.,
Centrohem, Serbia), H2O2 30% (p.a., Centrohem, Serbia), iron(III) ci-
trate (Acros Organics, USA), and zeolite HZSM-5 (Zeolyst International,
SiO2/Al2O3 = 30, SBET = 400 m2g-1) were used as received.
2.2. Synthesis of FeZSM-5 zeolite
FeZSM-5 zeolite was prepared via ion-exchange of HZSM-5 zeolite
[51]. The ion exchange procedure was conducted in suspension com-
prising 20 g HZSM-5 zeolite and 3 × 10−4 M iron(III) citrate in total
volume of 2 L. The suspension was stirred for 15 days and subsequently
the resulting FeZSM-5 was filtered, washed with deionized water and
dried at 110 °C.
2.3. Synthesis of PANIs and PANI/FeZSM-5 composites
Based on the procedure for preparation of PANI/ZSM-5 nano-
composites by the oxidative polymerization of aniline with APS in
water without added acid in the presence of ZSM-5 [23,25], in order to
obtain PANI/FeZSM-5 composite using the initial weight ratio aniline/
FeZSM-5 = 1/1, aqueous suspension comprising FeZSM-5 (1.86 g) and
aniline (1.86 g; 0.02 mol) was prepared, in a total volume of 50 mL. The
FeZSM-5/aniline aqueous suspension was stirred 10 min, subsequently
the 50 mL of APS solution in water (5.7 g; 0.025 mol) was poured to the
FeZSM-5/aniline aqueous suspension, and after constant stirring for
2 h at 23 °C the resulting PANI/FeZSM-5 composite material, denoted as
PFeZ1/1, was collected on a filter, washed with 0.005 M H2SO4, and
then dried in vacuo at 60 °C for 3 h. Similarly, the PANI/FeZSM-5
composite sample denoted as PFeZ1/5 was prepared by using the initial
weight ratio aniline/FeZSM-5 = 1/5. In both experiments, the molar
ratio aniline/APS was 1:1.25 and zeolite content in a reaction mixture
was set to 1.86 g. Pure PANI was synthesized by the same method
without the presence of zeolite. The initial pH values for FeZSM-5/
aniline suspensions were 8.72 and 8.80, for PFeZ1/1 and PFeZ1/5,
respectively. The pH values of reaction mixtures at the end of poly-
merization, after 45 min for PFeZ1/1 and 24 h for PFeZ1/5, were 0.7
and 1.8, respectively. In order to investigate the influence of the initial
acidity of reaction mixture on catalytic properties of prepared compo-
sites, PANI/FeZSM-5 composites were also prepared, using the same
synthetic procedure, by the chemical oxidative polymerization of ani-
line in aqueous FeZSM-5 suspension acidified by H2SO4, i.e., the
starting FeZSM-5/aniline aqueous suspension was made in 0.2 M H2SO4
instead of water. Composite samples obtained in acidified medium
using the initial weight ratios aniline/FeZSM-5 = 1/1 and 1/5 are de-
noted as PFeZ1/1S and PFeZ1/5S, respectively, while PANI sample
obtained in acidified medium without the presence of FeZSM-5 is de-
noted as PANI/S. The initial pH values for FeZSM-5/aniline/H2SO4/
APS suspensions were 2.4 and 1.3, for composites with the initial
weight ratio zeolite/aniline = 1 and 5, respectively. The overall time of
polymerization, tpol, of 25 min was set in order to achieve a value of
pH = 0.5–0.8 at the end of the reaction.
A portion of all prepared samples was treated with an excess of 5%
NH4OH for 3 h, to transform as-synthesized protonated PANI (salt) form
to deprotonated (base) form. The samples obtained by the base treat-
ment were collected on a filter, rinsed with 5% NH4OH, and dried in
vacuo at 60 °C for 3 h. Samples in deprotonated form were labeled with
suffix d.
M. Milojević-Rakić et al.
2.4. Characterization
The Al, Si and Fe content in the FeZSM-5 zeolite and PANI/FeZSM-5
composites were determined by Inductively Coupled Plasma-Optical
Emission Spectroscopy method (ICP-OES) on Thermo Scientific iCAP
6500 Duo Spectrometer. The emission lines were: Al (394.4 nm and
396.1 nm), Fe (239.5 nm and 259.9 nm) and Si (212.4 nm and
288.1 nm). Prior to analysis, the samples were subjected to microwave
digestion in ETHOS 1 Advanced Microwave Digestion System
(Milestone) with HPR-1000/10S rotor. Degradation involved two steps;
the first step included addition of 2 mL 96% H2SO4 and microwave
digestion program was set as 5 min heating to 150 °C with power output
of 1100 W. The second step involved consumption of 2 mL 65% HNO3,
1 mL 40% HF, and 2 mL 85% H3PO4, while microwave digestion pro-
gram was set as 10 min heating to 210 °C and 15 min heating at 210 °C,
with power output of 1100 W.
Morphology of PANI and PANI/FeZSM-5 composite samples was
investigated by JSM-6610LV (JEOL) scanning electron microscope. The
analyses were done under acceleration voltage of 15 kV, a beam current
of 20 nA and a spot size of 1 mm. Samples were coated by thin gold
layers using Leica EM SCD005 sputter coater.
Thermogravimetric analysis (TGA) and differential thermal analysis
(DTA) were performed by SDT 2960 (TA Instruments) thermoanalytical
device by heating the sample from room temperature to 800 °C in
synthetic air (5N) stream (flow rate 70 mLmin–1) at a heating rate of
10 °C/min.
FTIR spectra of the powdered samples, dispersed in KBr and com-
pressed into pellets, were recorded in the range 4000–400 cm−1 at 64
scans per spectrum with 2 cm−1 resolution using Nicolet 6700 FTIR
Spectrometer (Thermo Scientific).
Raman spectra of samples, excited with a diode-pumped solid state
laser (532 nm), were collected on a DXR Raman microscope (Thermo
Scientific) which is equipped with an Olympus optical microscope and a
CCD detector. The powdered sample was placed on an X–Y motorized
sample stage and the laser beam was focused on the sample using the
objective magnification of 50×. The scattered light was analyzed by
the spectrograph with a grating 900 lines mm−1 and a spectrograph
aperture of 50 μm slit. Laser power was kept at 0.2 mW on the sample.
Data manipulation was performed by integrated OMNIC software
package.
X-ray powder diffraction (XRPD) patterns were collected at room
temperature using a Philips PW-1710 automated diffractometer. The
instrument was equipped with a Cu anode (λCu Ka = 1.54178 Å), curved
monochromator and Xe-filed proportional counter. Diffraction data
were collected in the 3–70° 2θ range with a step size of 0.05 and a
counting time of 5.75 s for PANI/FeZSM-5 composites.
For conductivity measurements, the samples were pressed into
pellets between stainless pistons under a pressure of 124 MPa using a
hydraulic press. The conductivity was measured by means of an AC
bridge (Waynne Kerr Universal Bridge B 224), at fixed frequency of
1.0 kHz. All samples were dried in vacuo at 60 °C for 3 h before the
conductivity measurement.
2.5. Glyphosate degradation and quantitative HPLC analysis
The experiments which involved glyphosate removal in the pre-
sence of H2O2 were conducted at 23 °C. The reaction dispersions in-
cluded 20 mL of glyphosate standard (1 gL–1), 100 mg of sample (PANI
or PANI/FeZSM-5 composites, prepared in water or in H2SO4) and
120 μL H2O2 (30%, Fluka). The molar ratio glyphosate/H2O2 was in
accordance with optimal experimental conditions found in the litera-
ture [49]. The blank experiment involved the same experimental pro-
cedure in the system comprising only glyphosate and H2O2 without
probed PANI and composite samples. During 4 h of reaction, the ali-
quots were taken out from the reaction mixture at given time intervals,
centrifuged at 13,400 rpm (Minispin, Eppendorf), filtered through a
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Microporous and Mesoporous Materials 267 (2018) 68–79
0.45 μm Phenex nylon syringe filter and the amount of glyphosate
present in the supernatant was measured by high-performance liquid
chromatography (HPLC). The Bischoff chromatograph system consists
of a HPLC Compact Pump Model 2250 fitted with a LC-CaDI 22–14
Interface, sample injector and Gastorr TG-14 Degasser. The system and
the data management were controlled by MacDAcq integral software.
The stationary phase column was a Partisil SAX (Whatman),
250 × 4.6 mm, 10 μm particle diameter. The glyphosate determination
was performed by injecting 50 μL of solution into the chromatograph,
and the absorbance at 200 nm was then measured using UV/VIS
Lambda 1010 detector. The eluent was phosphate buffer:methanol
(96:4, v/v; pH = 1.9) isocratic mixture with a flow rate of 2 mLmin–1.
All solvents and analytes for HPLC were filtered through a 0.45 μm
nylon membrane filter. Ultra-high purity water obtained by a Milli-Q
water purification system (Millipore) was used throughout all HPLC
analyses. Additional glyphosate adsorption experiments were con-
ducted for all samples in the reaction system without H2O2.
3. Results and discussion
3.1. Temperature profiles of polymerization reactions
The temperature profiles for polymerization of aniline in the pre-
sence of FeZSM-5 in water, with and without added acid, are presented
in Fig. 1. The profile that corresponds to the preparation of the sample
PFeZ1/1 in water without added acid (Fig. 1 left) shows two exothermic
phases, separated by an athermal (induction) period, similar to the
curve found previously for composite sample prepared with HZSM-5
zeolite and aniline under the same experimental conditions [23]. The
addition of iron in zeolite ZSM-5 prolonged, to a small extent, start of
the second exothermic phase, that is, slowed down the polymerization
for about 6 min for PFeZ1/1 (≈20 min) in comparison to the equivalent
sample without iron ions (≈14 min) [23].
However, further increase of FeZSM-5 content in the composite
sample (synthesis of PFeZ1/5) leads to a transformation of the tem-
perature profile to only one existing exothermic phase, without in-
duction period (Fig. 1 right). In the temperature profile for PFeZ1/1S
composite prepared in the H2SO4 aqueous solution, only one exo-
thermic phase with preceding short induction period (≈8 min) is seen
(Fig. 1 left). Similarly to the syntheses without added acid (PFeZ1/1
and PFeZ1/5), increasing the initial weight ratio FeZSM-5/aniline
(PFeZ1/5S) resulted in complete absence of induction period (Fig. 1
right).
3.2. Morphology
SEM images of synthesized PANI/FeZSM-5 composite samples are
shown in Fig. 2. In Fig. 2a the morphologies of protonated composites
PFeZ1/1 and PFeZ1/5 (Fig. 2a left) and their deprotonated counterparts
PFeZ1/1d and PFeZ1/5d (Fig. 2a right) are compared, in addition to
morphologies of pure FeZSM-5 zeolite and pure PANI prepared in
water, without added acid.
The pure PANI contains nanorods/nanotubes in addition to the
granular and sheet-like objects (Fig. 2a), as it was observed previously
[23,25,52]. Nanorods (and possibly nanotubes) are also present in the
nanocomposites PFeZ1/1 and PFeZ1/5 as well as granules and ag-
glomerates. After the deprotonation of all composites, the morphology
of PFeZ1/1d and PFeZ1/5d (Fig. 2a, right) was not significantly
changed, although morphology seems more agglutinated in comparison
to the corresponding as-synthesized samples (Fig. 2a, left). The mate-
rials prepared in the solution of H2SO4, PFeZ1/1S and PFeZ1/5S, have
granular morphology, without the presence of 1-D nanostructures
(Fig. 2b, left), similar to pure PANI/S. There is no important difference
in the morphology of deprotonated samples PFeZ1/1Sd and PFeZ1/5Sd
(Fig. 2b, right) related to their protonated counterparts. Fig. 2 gives also
evidence that there is not a great variation in morphological structures
M. Milojević-Rakić et al. Microporous and Mesoporous Materials 267 (2018) 68–79

Fig. 1. Temperature changes during the oxidation of aniline with APS in water and in aqueous solution of H2SO4 for the syntheses of PFeZ1/1 (left) and PFeZ1/5 (right) composites.

Fig. 2. SEM micrographs of protonated and deprotonated PANI/FeZSM-5 composites prepared a) in water, without added acid, and b) in aqueous solution of H2SO4. Micrographs of pure
FeZSM-5 and pure PANIs prepared in water and in the H2SO4 aqueous solution are also given.

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Fig. 3. TGA curves for a) protonated and c) deprotonated forms of PANI/FeZSM-5 composites, and DTA curves for b) protonated and d) deprotonated forms of PANI/FeZSM-5 composites.
TGA and DTA curves for FeZSM-5 zeolite are also presented.

for PANI/FeZSM-5 composites in comparison to corresponding com- adsorbed water [23]. For pure FeZSM-5, after releasing adsorbed water,
posites prepared with HZSM-5 zeolite which were previously in- there is practically no weight loss at temperature higher than c.a. 200 °C
vestigated [25]. (Fig. 3a). It means that the structure of the zeolite is sustained up to
800 °C and the overall thermal changes in the composites at tempera-
ture higher than c.a. 200 °C can be predominantly attributed to its PANI
3.3. Thermogravimetric analysis part. The main weight loss of the composite samples occurs in the
temperature interval ≈300–600 °C and is attributed to the degradation
TGA/DTA curves for protonated and deprotonated composites pre- and decomposition of PANI backbone [53]. It can be observed that
pared in water and in aqueous H2SO4 solution, as well as for pure FeZSM-5/PANI weight ratio in composite samples (Table 1) corre-
FeZSM-5, are given in Fig. 3. Content of FeZSM-5, PANI and water in sponds well to the initially applied weight ratio FeZSM-5/aniline (1 and
composites, as well as the weight ratio FeZSM-5/PANI in composites, 5), similarly to results obtained for PANI/HZSM-5 composites without
determined by TGA, are shown in Table 1. This determination was iron ions [23]. This is particularly valid for the deprotonated form of
based on the following facts: the combustion of PANI in air stream is samples from which sulfate and hydrogensulfate counter-ions were
completed at 640 °C, the residual weight upon heating refers to the removed (see Scheme 1) and only polymer backbone from PANI part is
content of zeolite in the composite, and the weight loss from room present in the composite samples. The obtained variance in water
temperature to c.a. 200 °C corresponds mainly to the release of content could be described by different quantities of water in PANI and
zeolite parts of the composites. In DTA curves, an endothermic peak is
Table 1 observed at about 50 °C for composites and pure FeZSM-5 (Fig. 3b and
Content of FeZSM-5, PANI and water in protonated and deprotonated PANI/FeZSM-5
composites, prepared in water and in aqueous solution of H2SO4, and weight ratio FeZSM-
d), attributed to the release of residual/adsorbed water [53]. An exo-
5/PANI, determined by TGA. thermic hump at DTA curves of composites observed at about 200 °C
can be related to cross-linking reactions of PANI chains, while strong
Sample Content (wt.%) Weight ratio and broad peak with maxima at about 400, 500 and 550 °C corresponds
FeZSM-5/PANI
to the thermal oxidative degradation and combustion processes of PANI
FeZSM-5 PANI H2O
part. These maxima are probably related with macromolecules having
PFeZ1/1 43.1 52.2 4.7 0.83 significantly different molecular weights [53]. In the region 400–600 °C
PFeZ1/1d 47.4 48.4 4.2 0.98 the DTA curve is simplest (only one noticeable maximum at about
PFeZ1/5 77.9 18.1 4.0 4.30
500 °C) for samples PFeZ1/5 and PFeZ1/5d.
PFeZ1/5d 78.9 15.0 6.1 5.26
PFeZ1/1S 42.2 51.6 6.2 0.82
PFeZ1/1Sd 47.2 48.4 4.4 0.98
3.4. Elemental analysis
PFeZ1/5S 76.9 16.8 6.3 4.58
PFeZ1/5Sd 79.4 15.5 5.1 5.12
The elemental composition of synthesized PANI/FeZSM-5

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Table 2 Table 4
Elemental composition (N, C, H and S) of PANI/FeZSM-5 composites in their protonated Conductivity of PANI/FeZSM-5 composites, pure PANI and PANI/
and deprotonated forms, determined by elemental microanalysis. S samples.

Sample Content (%) N/C Sample Conductivity (Scm−1)

N C H S PFeZ1/1 1.2 × 10−3

PFeZ1/1S 1.7 × 10−2
PANI 11.1a 55.4a 4.4a 6.3a 0.2 PFeZ1/5 7.4 × 10−6
PFeZ1/1 6.1 31.9 2.8 2.8 0.2 PFeZ1/5S 1.1 × 10−5
PFeZ1/5 2.2 11.7 1.4 0.4 0.2 PANI 3.3 × 10−3
PANI/S 11.4a 55.4a 4.3a 6.0a 0.2 PANI/S 7.3 × 10−3
PFeZ1/1S 6.2 32.3 3.1 3.3 0.2
PFeZ1/5S 1.9 11.1 1.5 0.4 0.2
PANId 13.4a 70.1a 4.4a 0.7a 0.2 account low conductivity of inorganic component, zeolite.
PFeZ1/1d 7.1 34.4 2.9 0.9 0.2
PFeZ1/5d 2.6 9.9 1.5 / 0.3
PANI/Sd 14.8a 74.8a 4.9a 0.6a 0.2 3.6. FTIR spectroscopy
PFeZ1/1Sd 7.6 37.0 3.0 / 0.2
PFeZ1/5Sd 2.7 10.8 1.6 / 0.3
3.6.1. FTIR spectroscopy of as-synthesized PANI/FeZSM-5 samples
a
Values taken from reference [25]. The FTIR spectra of as-synthesized (protonated) samples PANI,
PFeZ1/1, PFeZ1/5, PANI/S, PFeZ1/1S and PFeZ1/5S are presented in
composites in both protonated (as-synthesized) and deprotonated forms Fig. 4. Characteristic bands of PANI salt are positioned in these spectra
is presented in Table 2. The N/C wt.% ratio takes the value of ≈0.2 in at 1593–1573 cm−1 (the ring C–C stretching vibrations in polaronic
the as-synthesized composites, prepared in water and in H2SO4, and –NH•+–C6H4– and/or bipolaronic –NH+=C6H4═NH+ = structures, Q-
increases upon the deprotonation to 0.3 for PFeZ1/5d and PFeZ1/5Sd band), 1497–1483 cm−1 (the ring C–C stretching vibration in the
composites. The N/C wt.% ratio for the deprotonated composites also structure –NH–C6H4–NH–, B-band), 1309–1295 cm−1 (the C–N
increases with the increase of zeolite content in the composite (from 0.2 stretching vibration of secondary aromatic amine) and 823–818 cm−1
for PFeZ1/1d and PFeZ1/1Sd to 0.3 for PFeZ1/5d and PFeZ1/5Sd). This (out-of-plane deformation C–H vibration of 1,4-disubstituted benzene
increment could be explained by the reaction of NH3 (used for the rings in linear chains, γ(C–H)1,4) [54–60].
deprotonation) with protons (unsubstituted by Fe) in the zeolite extra- Further on, the bands assigned to the stretching of phenazine units,
framework positions, leading to NH4+ ions attached to the zeolite formed by the oxidative cyclization reaction of branched oligoaniline
framework in the composite [25], that is noticeable only in PANI/ and PANI chains, are present in the spectra of samples PANI and PFeZ1/
FeZSM-5 composites with high content of zeolite. The Al, Si and Fe 1, prepared in water, at 1416 cm−1 [54,56,59,60]. This band is not
contents in the FeZSM-5 zeolite and PANI/FeZSM-5 composites de- detected in the spectrum of PFeZ1/5 and in the spectra of all samples
termined by ICP-OES are given in Table 3. The Fe content in FeZSM-5 prepared in the solution of H2SO4 (PANI/S, PFeZ1/1S and PFeZ1/5S).
zeolite is found to be 0.11 wt %, for as-synthesized composites PFeZ1/1 The band characteristic for monosubstituted aromatic ring (out-of-
and PFeZ1/1S it amounts to 0.04, while for PFeZ1/5 and PFeZ1/5S plane ring deformation) [54], indicative for chain terminals and/or N-
composites content of Fe is found to be 0.08 and 0.06 wt%, respectively. phenylphenazinium units, i.e. for the presence of oligomers and
branching [52,55,61,62], is positioned at 686–710 cm−1 for all samples
3.5. Conductivity measurements prepared in water. This band has lower intensity in the spectra of
samples prepared in the presence of H2SO4 suggesting longer chains
Table 4 shows data on the electrical conductivity of the investigated with smaller amount of branches in these samples compared to samples
samples (in protonated forms). The synthesis procedure in water, prepared in water.
without added acid, produces conducting form of PFeZ1/1 with con- The characteristic bands of FeZSM-5 zeolite in the spectra of com-
ductivity of 1.2 × 10−3 S/cm, of the same order of magnitude as pure posites PFeZ1/1, PFeZ1/5, PFeZ1/1S and PFeZ1/5S are positioned at:
PANI (3.3 × 10−3 S/cm). The samples prepared in the aqueous solution 1228–1223 cm−1 (external tetrahedron linkages-asymmetric
of H2SO4 (PANI/S, PFeZ1/1S and PFeZ1/5S) express higher con- stretching), 1106–1092 cm−1 (internal tetrahedron linkages-asym-
ductivity values when compared to the corresponding samples prepared metric stretching). 797–802 cm−1 (the symmetric stretching vibration
in water without added acid (PANI, PFeZ1/1 and PFeZ1/5). The in- of external linkages in zeolite), 618–620 cm−1, 588–582 cm−1 and
crease of zeolite content in composites leads to decrease of conductivity 544–543 cm−1 (vibrations of double five-membered rings of tetrahedra
by about three orders of magnitude and to lighter shades of green color in the zeolite framework) and 456–454/447–444 cm−1 (T–O bending,
of samples. This decrease of conductivity is expectable, taking into T = Si or Al, internal tetrahedron) [23,63,64]. The positions of these
bands correspond to those in the FTIR spectrum of pure FeZSM-5 that
Table 3 are located at 1225, 1099, 794, 619, 582, 546 and 459/449 cm−1
Elemental composition (Al, Fe and Si) of PANI/FeZSM-5 composites in their protonated (Fig. 4). There are no significant differences, rather minor shifts in
and deprotonated forms and FeZSM-5 zeolite, determined by ICP-OES. comparison to the FTIR spectrum of HZSM-5 zeolite [25], attributed to
the presence of iron in the zeolite. The bands observed in the spectra of
Sample Content (%) Si/Al
composites at about 820 and 800 cm−1 are due to mixed contributions
Al Fe Si of the symmetric stretching vibration of external linkages in zeolite and
the γ(C–H)1,4 vibration in PANI chains. The relative intensities of PANI
PFeZ1/1 1.33 0.04 14.34 10.8 bands decrease with decreasing PANI content in the composites, as
PFeZ1/5 2.67 0.08 38.70 14.5
PFeZ1/1S 1.31 0.04 19.42 14.8
expected.
PFeZ1/5S 2.89 0.06 43.25 15.0 The bands that are attributed to B–NH+ = Q stretching with con-
PFeZ1/1d 1.54 0.05 12.09 7.9 tribution of asymmetric SO3 stretching in HSO4− anion, indicative for
PFeZ1/5d 2.38 0.07 40.47 17.0 good electrical conductivity, are detected at 1144 and 1108 cm−1 in the
PFeZ1/1Sd 1.45 0.04 26.80 18.5
spectrum of PANI and at 1140 cm−1 (shoulder) and 1106 cm−1 in the
PFeZ1/5Sd 2.66 0.07 45.71 17.2
FeZSM-5 3.46 0.11 54.74 15.8 spectrum of PANI/S. In the case of composite samples, these bands are
located at 1144 (shoulder)/1099 and 1146/1106 cm−1 for PFeZ1/1

73
M. Milojević-Rakić et al.
Fig. 4. FTIR spectra of protonated PANI and PANI/S samples, PANI/FeZSM-5 composite samples and FeZSM-5 zeolite. Bands marked with (*) are assigned to the zeolite component of the
composites.
and PFeZ1/1S, respectively, while in the spectra of composite samples
with higher amount of zeolite, PFeZ1/5 and PFeZ1/5S, these bands are
most likely overlapped with the strong zeolite band at about
1100 cm−1. In the spectra of all protonated materials, the bands as-
signed to counter-ions attached to PANI matrix are located at
884–879 cm−1 (HSO4−) and 620–616 cm−1 (HSO4− and/or SO42−).
The band positioned at c.a. 620 cm−1 in the spectra of composites is
due to the combination of stretching vibration modes ascribed to PANI
counter-ions and ring vibrations of tetrahedra in the zeolite. The shift of
several bands is observed with the increase of zeolite content in the
samples. Q-band and B-band express the blue-shift with the increase of
zeolite content: from 1573 and 1494 cm−1 for PFeZ1/1 to 1593 and
1497 cm−1 for PFeZ1/5. On the other hand, the bands ascribed to
asymmetric stretching of external tetrahedron and T–O bending in in-
ternal tetrahedron of zeolite framework exhibited the red shift with the
increase of zeolite content and are positioned at 1227 cm−1 and
74
Microporous and Mesoporous Materials 267 (2018) 68–79
456 cm−1 for PFeZ1/1 and at 1224 cm−1 and 455 cm−1 for PFeZ1/5.
There is a similar situation for composite samples prepared in the
presence of H2SO4 – the blue shift of Q-band and B-band (from 1576
and 1483 cm−1 for PFeZ1/1S to 1577 and 1497 cm−1 for PFeZ1/5S)
and the red shift of zeolite band (1228 cm−1 for PFeZ1/1S and
1223 cm−1 for PFeZ1/5S). These shifts might be due to more pro-
nounced interactions of PANI chains and zeolite with the increase of
FeZSM-5 content in the composites. Possible types of interactions are:
electrostatic attraction of positively charged PANI chains with nega-
tively charged alumosilicate surface, hydrogen bonding, ion-dipole and
dipole-dipole interactions [23,25].
3.6.2. FTIR spectroscopy of deprotonated PANI/FeZSM-5 samples
After the samples were treated with alkali, a number of bands in the
FTIR spectra of the deprotonated samples (Fig. 5) appear shifted in
comparison to the bands in the spectra of protonated samples.
M. Milojević-Rakić et al.
Fig. 5. FTIR spectra of deprotonated PANI and PANI/S samples and PANI/FeZSM-5 composites. Bands marked with (*) are assigned to the zeolite component of the composites.
Conversion of PANI salt to its base form is apparent by inspection of the
Q-band and B-band shifts. The Q-band is blue-shifted upon deproto-
nation, in order: 1573 → 1589 (PFeZ1/1→PFeZ1/1d), 1593 → 1600
(PFeZ1/5→PFeZ1/5d), 1576 → 1594 (PFeZ1/1S→PFeZ1/1Sd) and
1577 → 1592 cm−1 (PFeZ1/5S→PFeZ1/5Sd). The B-band exhibited
also blue-shifting upon alkali treatment: 1494 → 1507 (PFeZ1/1→
PFeZ1/1d), 1497 → 1507 (PFeZ1/5→PFeZ1/5d), 1483 → 1499
(PFeZ1/1S→PFeZ1/1Sd) and 1497 → 1507 cm−1 (PFeZ1/5S→PFeZ1/
5Sd). These shifts are representative for PANI salt to base form trans-
formations and are due to the transformations of C6H4 rings in po-
laronic (semiquinonoid) and bipolaronic (protonated quinonoid, dica-
tionic) structures of protonated forms to quinonoid rings in
–N=C6H4 = N– structures of deprotonated forms. This feature shows
that PANI component has been deprotonated successfully in the pre-
sence of FeZSM-5 in the composites.
The new band, typical for the PANI emeraldine base, assigned to
C–N stretching in QBtQ units (Bt denotes a trans benzenoid unit), is
detected in the spectra of PFeZ1/1Sd and PFeZ1/1d at 1380 and
75
Microporous and Mesoporous Materials 267 (2018) 68–79
1379 cm−1, respectively [55,62]. The band ascribed to phenazine type
units is seen in the FTIR spectra of deprotonated samples PFeZ1/5d,
PFeZ1/1Sd and PFeZ1/5Sd at 1400 cm−1, with the exception of spec-
trum recorded for PFeZ1/1d composite, where two bands are seen at
1400/1415 cm−1. The relative intensity of band at c.a. 1400 cm−1 at-
tributed to phenazine units decreases with the decrease of zeolite
content for all the deprotonated composites. As observed in the spectra
of protonated samples, the band due to the monosubstituted aromatic
rings, at 692–696 cm−1, is much more intense for deprotonated PANI
and deprotonated composites prepared in water than for the corre-
sponding samples prepared in sulfuric acid (Fig. 5).
3.7. Raman spectroscopy of PANI and PANI/FeZSM-5 samples
The Raman spectra of protonated PANI and PANI/FeZSM-5 samples
(Fig. S1) show the bands characteristic for structural segments of pro-
toemeraldine/emeraldine/nigraniline salt [65] positioned at:
1599‒1584 cm−1 (C=C and C ∼ C stretching vibrations of the Q and
M. Milojević-Rakić et al.
SQ rings, ν(C=C)Q and ν(C ∼ C)SQ, respectively), 1541‒1535 cm−1 for
samples prepared without acid and 1524‒1508 cm−1 for samples pre-
pared in the presence of H2SO4 (N–H bending vibrations),
1344‒1340 cm−1 (C ∼ N+• stretching vibrations in polaronic struc-
ture), 1258‒1251 cm−1 (C–N stretching in B units) and
1178‒1173 cm−1 (C–H bending in-plane vibrations of SQ rings,
δ(C–H)SQ). When we study Raman spectra of the samples prepared in
water, without added acid, the band ν(C=C)Q/ν(C ∼ C)SQ is moved to
lower wavenumber with increase of zeolite content in the investigated
materials: 1594 cm−1 (PANI) → 1592 cm−1 (PFeZ1/1) →1584 cm−1
(PFeZ1/5). This shift could be explained by the decrease of SQ (po-
laronic) form contribution and/or the reduction of protonation degree
in polymer chains, in sequence from PANI toward PFeZ1/5 [52]. A si-
milar change, although less pronounced, could be seen in the spectra of
samples prepared in the solution of H2SO4: 1599 cm−1 (PANI-S) →
1597 cm−1 (PFeZ1/1S and PFeZ1/5S). Deprotonation of the samples
leads to appearance of the bands characteristic for PANI base form,
along with observable change in the position of several bands. The band
assigned to C=N stretching in Q units, ν(C=N)Q, appears as dominant,
strong band in the spectra of deprotonated materials, at wavenumbers
in the range 1484–1472 cm−1 (Figs. S1 and S2). The exception is the
spectrum of PFeZ1/5d sample, where this band is strong but not
dominant, that could be an indication of lower content of Q units (lower
oxidation degree) in this sample. The relative intensity of ν(C=N)Q
band decreases with the increase of zeolite content in the samples (Figs.
S1 and S2).
Deprotonation of the samples leads to displacement of the δ(C–H)
band toward lower wavenumber in comparison to its position in spectra
of protonated samples, as a result of SQ to Q ring transformation:
1178 cm−1 (PANI)→1167 cm−1 (PANId), 1173 cm−1 (PFeZ1/1) →
1166 cm−1 (PFeZ1/1d), 1175 (PANI/S) → 1163 (PANI/Sd), 1174 cm−1
(PFeZ1/1S) → 1165 cm−1 (PFeZ1/1Sd) and 1178 cm−1 (PFeZ1/5S) →
1166 cm−1 (PFeZ1/5Sd).
The sample PFeZ1/5 is excluded from this band arrangement since
δ(C–H) band is located at 1183 cm−1; this band position is more related
to B rings [52] and remains unchanged upon deprotonation. In general,
the minor changes after deprotonation were observed for PFeZ1/
5 − PFeZ1/5d pair, their spectra are very similar. This result indicates
relatively low protonation degree in PFeZ1/5 sample; therefore, the
treatment with alkali induced no measureable effect on its structure.
The bands assigned to phenazine type segments can be seen in the
spectra of protonated and deprotonated PANI and PANI/FeZSM-5
samples at 1636‒1628 cm−1 (with contributions of C ∼ C stretching
vibrations in B units), 1567‒1556 cm−1, 1412–1405/1394‒1392 cm−1
(for samples prepared in the presence of H2SO4 there is only the first
Fig. 6. Kinetic curves for glyphosate decomposition with H2O2 (percent of the remaining glyphosate as a function of time) in the presence of investigated PANI and PANI/FeZSM-5
composites prepared in water (left) and in the solution of H2SO4 (right).
76
Microporous and Mesoporous Materials 267 (2018) 68–79
band), ≈1360 cm−1 for samples prepared in water without acid, and
1340 cm−1 for samples prepared with acid.
In the spectrum of pure FeZSM-5 (Fig. S1), characteristic bands of
zeolite ZSM-5 [57,59,66] are poorly visible, due to the strong fluores-
cence, and the software correction did not lead to noticeable im-
provement. The presence of PANI in the composite samples decreased
fluorescence to some extent. However, characteristic bands of ZSM-5
zeolite in composites spectra which are expected in the 1200‒200 cm−1
region are overlapped with higher intensity PANI bands. The experi-
mental conditions (low laser power) were optimized in order to avoid
carbonization of the PANI in the composite samples which resulted in
low intensity of zeolite bands.
3.8. X-ray diffraction
Diffractograms of as-prepared and deprotonated PANI/FeZSM-5
composites are presented in Fig. S3. XRPD patterns of the samples
prepared with initial weight ratio PANI/FeZSM-5 of 1/1 showed broad
profile due to amorphous structure in the polymer part of the compo-
site. Nevertheless, the low intensity reflexion is recorded for the PFeZ1/
1 and PFeZ1/1d samples at 2θ angles of 6.5° and 6.45°, respectively.
Previously, we reported the strong and very sharp reflexion at 6.6° for
the nanostructured PANI, while weaker reflexion was observed at 6.4°
for granular PANI/S [25]. This peak has been associated with the or-
dering of counter ions in PANI matrix, and its position depends on the
doping level of PANI [53]. It is interesting that in diffractograms of
composites PFeZ1/1S and PFeZ1/1Sd (Fig. S3) the reflexion at this 2θ
angle is not seen. The composite samples with higher zeolite content
(PANI/FeZSM-5 = 1/5) give patterns which point to preservation of the
zeolite crystallographic structure upon aniline polymerization. As a
consequence of relatively small amount of PANI in these composite
samples, there is no broad profile typical for PANI structure [23,25].
3.9. Catalytic degradation of glyphosate in the presence of H2O2 by PANI
and PANI/FeZSM-5 composites as catalysts
Kinetic curves for catalytic removal of glyphosate in the presence of
H2O2 and PANI, PANI/S and PANI/FeZSM-5 composites are given in
Fig. 6. All investigated materials were catalytically active in this se-
lected oxidation reaction. As observed from Fig. 6, the best catalyst
performance was found for samples synthesized without added acid,
PFeZ1/5 (80.4%), PANId (56.6%) and PFeZ1/1 (40.8%), and their
pseudo-first order rate constants have highest values (Table 5). As re-
moval process is comprised of competitive processes, oxidative de-
gradation and adsorption (examined in the equivalent experimental
M. Milojević-Rakić et al. Microporous and Mesoporous Materials 267 (2018) 68–79

Table 5 glyphosate probe. Preparation procedure and interactions in these

pH value of catalyst sample suspensions (PANI, PANI/FeZSM5 composites and FeZSM-5 composite materials provide efficient electron transfer and H2O2 de-
zeolite) with glyphosate and H2O2 at the beginning of the reaction and after 4 h of re-
gradation, which was found to be crucial for advanced catalytic per-
action time. The percent of the removed and decomposed glyphosate in catalytic reaction
system with investigated materials after t = 4 h and pseudo-first order removal rate formance of several investigated PANI/FeZSM-5 composites.
constant, k, are shown. Literature data suggest that the combination of hydrogen peroxide
and UV irradiation could be a suitable option for decreasing glyphosate
Sample pH % glyphosate % glyphosate k(min−1)‧ 104 concentration to acceptable limits. Under optimal conditions, total or-
removed decomposed
t=0 t=4h
ganic carbon (TOC) conversion after 5 h was reported to be 70% in UV
radiation-supported reaction comprising 0.30–0.45 mM glyphosate
PFeZ1/5Sd 2.8 2.5 3.8 0 1.8 ± 0.1 (76 mgL−1) [49]. Huston and Pignatello reported 35% decrease of total
PANI/Sd 2.6 2.2 6.6 2.8 2.5 ± 0.5 organic carbon following 2 h photo‒Fenton treatment of low glyphosate
PFeZ1/1Sd 2.8 2.6 7.4 1.1 2.9 ± 0.7
PANI/S 2.3 2.2 10.2 9.7 4.6 ± 0.7
concentration solution (34 mgL−1) [41]. Photodegradation of glypho-
PANI 3.0 2.9 12.4 11.6 6±2 sate in the ferrioxalate system was found to be dependent on initial
FeZSM-5 3.1 3.0 12.8 7.1 5±1 concentrations of glyphosate (1‒4 mgL‒1) and ferric‒ions/oxalate ra-
PFeZ1/1d 3.3 2.8 13.6 8.4 6±1 tios. At acidic pH value, in the range of 3.5–5.0, high efficiency of or-
PFeZ1/5S 3.0 2.8 18.1 13.6 9±3
thophosphates release due to glyphosate (5 mgL−1) degradation, up to
PFeZ1/5d 3.1 2.9 20.4 14.6 9±1
PFeZ1/1S 3.0 2.9 26.8 22.6 13 ± 3 60.6%, was achieved. Two degradation paths were proposed, namely,
PFeZ1/1 3.4 3.0 40.8 31.9 24 ± 9 cleavage of C–N in the first and the splitting of C–P bonds in the second,
PANId 3.0 2.9 56.6 45.4 36 ± 3 both attributed to the action of radical species. In the former case,
PFeZ1/5 3.8 3.7 80.4 66.5 70 ± 10 glyphosate decomposes into aminomethylphosphonic acid and acetic
acid, while in the later, it is broken down to sarcosine and phosphoric
acid [67].
settings, without H2O2), the percent of adsorption-corrected glyphosate
The comparison among reported glyphosate removal efficiencies
degradation is given in Table 5 for each sample. An adsorption route is
may give speculative assessment since catalytic findings depend on
found to be minor for samples with highest removal rate, where the
various factors including catalyst type, solution acidity, initial con-
oxidative degradation rather than glyphosate adsorption is dominant
centration of pesticide and oxidant, equilibration time and overall ex-
pathway in overall process.
perimental conditions. Nonetheless, we employed here higher initial
Pure FeZSM-5 zeolite showed moderate catalytic activity in gly-
glyphosate concentration (1000 mgL−1) than previously reported
phosate removal (13% glyphosate was removed after 4 h) while even
[41,49,67] and accomplished 80% of pesticide removal from the aqu-
lower efficiency was found for PANI, PANI/S and PANI/Sd. Low re-
eous suspensions in 4 h reaction time, without implementation of UV
moval rates were also found for deprotonated composites prepared in
irradiation.
acidified solution, PFeZ1/5Sd and PFeZ1/1Sd (Table 5) where ad-
sorption was dominant in the mechanism of removal. Deprotonated
composites prepared in water, PFeZ1/5d (20.5% glyphosate removal)
4. Conclusions
and PFeZ1/1d (14% glyphosate removal) were more active when
compared to FeZSM-5 zeolite in the same 4 h period. The protonated
The nanostructured and granular PANIs and their composites with
composites prepared in aqueous H2SO4, PFeZ1/1S (28%) and PFeZ1/5S
FeZSM-5 zeolite were synthesized by the oxidative polymerization of
(18%), expressed improved catalytic activities than their deprotonated
aniline in water, without added acid, and in an aqueous H2SO4 solution.
forms. The interesting result is that the catalyst PFeZ1/5, with the
These novel composite materials in their protonated and deprotonated
highest zeolite and iron amount (0.08%) amongst composites expressed
forms were analyzed by a number of characterization techniques, and
the best catalytic activity in spite the fact that FeZSM-5 zeolite itself
were investigated as catalysts in glyphosate oxidation/decomposition
showed rather poor activity.
reaction in the presence of H2O2. All investigated composites were
The advanced catalytic performance of the composite samples is
catalytically active and their performance was compared to PANIs
observed as exceptionally large amount of glyphosate was oxidized in
samples and starting zeolite FeZSM-5. The improvement of catalytic
this process. For the same experimental conditions, the highest amount
activity for glyphosate oxidation was found for PANI/FeZSM-5 com-
of removed glyphosate was 16 mg for PFeZ1/5 sample, in the reaction
posites when compared with pure zeolite FeZSM-5, indicating synergic
suspension of 20 ml volume comprising 100 mg of catalyst, which re-
effect of PANI chains and zeolite in the composites that provides more
presents 160 mg of glyphosate per gram of composite sample. When we
efficient electron transfer and H2O2 degradation needed for efficient
inspect results regarding glyphosate adsorption on the same sample it
oxidation/degradation of glyphosate. In the presence of composite
could be noted that 27.8 mg of glyphosate was adsorbed per gram of
prepared in water using the initial weight ratio aniline/FeZSM-5 = 1/5
composite sample similar to 33.7 mg/g found for corresponding PANI/
(i.e., the composite which contains ≈78 wt% FeZSM-5 and ≈18 wt%
HZSM-5 composite sample without iron ions [25].
PANI), the maximum glyphosate amount which was removed in this
The initial pH value of the reaction suspension containing PFeZ1/5
process was achieved (160 mg per gram of catalyst). Besides excep-
(Table 5) was pH = 3.8 and after 4 h reaction time pH = 3.7, hence it is
tional performance of this composite (80.4% removed glyphosate in
evident that the largest amount of glyphosate was decomposed in the
4 h), a very good catalytic behavior exhibited also the deprotonated
system where mono-anionic glyphosate form [25] is dominant. The
PANI (56.6% removed glyphosate) and the composite prepared at in-
obtained kinetic results point to advanced catalytic performance of
itial weight ratio aniline/FeZSM-5 = 1/1 (40.8% removed glyphosate),
synthesized composites, i.e. synergic effect of PANI chains and zeolite
all materials prepared in water without added acid. It can be concluded
part of the composite sample. Higher zeolite content in the composites
that advanced catalytic performance of synthesized PANI/FeZSM-5
and therefore quantity of iron ions active for H2O2 degradation and
composites is influenced by synthetic procedure, relative content of
glyphosate oxidation could explain better activity of PFeZ1/5 compo-
zeolite and PANI components in composites, and interactions in this
site then PFeZ1/1 composite sample, both prepared in water. However,
complex system containing catalyst, pesticide and H2O2. The obtained
blank experiment showed that H2O2 without solid catalyst sample could
results suggest that PANI/FeZSM-5 zeolites are prospectus materials for
degrade only 14% of 1000 mgL−1 glyphosate standard in the 4 h
pesticide degradation in wastewater treatment.
period. Therefore, free radical scavenging activity could be presumed
for samples with lower removal rate than found for blank H2O2/

77
M. Milojević-Rakić et al.
Acknowledgments
The authors thank the Ministry of Education, Science and
Technological Development of the Republic of Serbia (grant numbers
OI 172043 and OI 172018) for financial support.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://dx.
doi.org/10.1016/j.micromeso.2018.03.019.
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