Chemosphere 241 (2020) 124981

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Complete removal of endocrine disrupting compound and toxic dye by

visible light active porous g-C3N4/H-ZSM-5 nanocomposite
Aanchal a, Sanghamitra Barman b, *, Soumen Basu a, **
a
School of Chemistry and Biochemistry, Thapar Institute of Engineering and Technology, Patiala, 147004, India
b
Department of Chemical Engineering, Thapar Institute of Engineering and Technology, Patiala, 147004, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

g-C3N4/H-ZSM-5 composite was

synthesized by facile calcination
method.

Fipronil and Methylene blue were
degraded to test the photocatalytic
activity.

Maximum photodegradation was
obtained by optimizing reaction
conditions.

Scavenger study was performed to
find the responsible species for
degradation.

a r t i c l e i n f o a b s t r a c t

Article history: Photocatalytic degradation of toxic pollutants is an efficient technique to completely remove the toxic
Received 4 July 2019 pollutants from water bodies. In the present investigation, photocatalytic degradation of pollutants was
Received in revised form studied over porous g-C3N4/H-ZSM-5 nanocomposite under visible light irradiation. The composite g-
23 September 2019
C3N4/H-ZSM-5 was synthesized by mixing an aqueous solution of H-ZSM-5 zeolite (increases surface
Accepted 26 September 2019
Available online 7 October 2019
area and provides active sites for degradation) with melamine (precursor of g-C3N4) for 10e12 h followed
by calcinations at 550  C. The photocatalyst was characterized by XRD, BET, HRTEM, FESEM, EDS and
Handling Editor: Jun Huang elemental mapping analysis. These techniques confirmed that, g-C3N4/H-ZSM-5 composite have layered
and porous structure with uniform distribution of g-C3N4 on H-ZSM-5 surface. The BET N2 adsorption-
Keywords: desorption analysis verified that the catalyst has high surface area (~175 m2/g) having mesopores and
Fipronil micropores. The prepared catalyst was then used for the photodegradation of a model dye, Methylene
Dye Blue (MB) and an endocrine disrupting compound, Fipronil (FIP). Effects of various parameters such as
Photocatalytic degradation pH, catalyst dose and scavengers were also studied. The % photocatalytic degradation of MB and FIP were
g-C3N4/H-ZSM-5 nanocomposites
around ~92% and ~84% with a high rate constants of 0.00997 and 0.00875 min1, respectively. From the
Zeolite
scavenger study, OH
(hydroxyl radical) and radical was found to be the major reactive species for
MB and FIP degradation. From these studies it is revealed that, the catalyst is visible active, easy to
prepare and an efficient photocatalyst for toxic pollutant degradation.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction

* Corresponding author. Rapidly growing industrialization has become a major concern

** Corresponding author.
worldwide as the industrial discharge into the environment is
E-mail addresses: sbarman@thapar.edu (S. Barman), soumen.basu@thapar.edu
(S. Basu). directly affecting the water bodies, wildlife and human (Raman and

https://doi.org/10.1016/j.chemosphere.2019.124981
0045-6535/© 2019 Elsevier Ltd. All rights reserved.
2 Aanchal et al. / Chemosphere 241 (2020) 124981
Kanmani, 2016). The increased pollution in the surrounding is due
to the effect of organic pollutants like dyes and Endocrine Dis-
rupting Compounds (EDCs), pharmaceuticals and many other
contaminants (Ji et al., 2017; Bolong et al., 2009). These are mainly
emitted with the industrial effluent water into the water bodies.
The dyes present in the wastewater makes it colored due to pres-
ence of aromatic rings in the structure of organic dyes and are
having hazardous effects on the environment (Kaur et al., 2019;
Lemlikchi et al., 2012). EDCs are also having harmful effects as they
mimic the functions of endocrine system of human beings and
wildlife, and it cause various unwanted problems like reproductive,
cardiovascular, metabolic and neurological disorders (Chang et al.,
2012).
Many different conventional treatment processes have been
adopted for the removal of organic pollutants from waste water
such as nano-filtration, adsorption, photocatalytic degradation,
biodegradation, membrane separation and advanced oxidation
process (Goyal et al., 2018; Bhunia and Jana, 2014; Wang et al.,
2019). Photocatalytic degradation is the most useful process as it
completely decomposes or removes the organic pollutants from the
environment. In recent years this process has been favorable from
others as it can utilize solar light energy (includes visible light) that
can be suitable for visible active materials and helps in degradation
of organic pollutant (Gong et al., 2013; Xu et al., 2015). Different
adsorbents have been used for the decontamination of toxic
organic pollutants like activated carbon (Yu et al., 2014), cellulose-
based materials (Tapia-Orozco et al., 2016), modified carbon
nanotubes (Ramana et al., 2013), porous metal oxide materials
(Sharma et al., 2017), clay materials (Mishra et al., 2017a), zeolites
(Goyal et al., 2018), etc.
In midst of the adsorbents zeolite is the best for its wide avail-
ability, high surface area, porous nature and reusability that makes
it suitable for the environmental applications like wastewater
treatment (Goyal et al., 2018). Due to these properties it has been
chosen as a support for graphitic carbon nitride (g-C3N4) for the
photodegradation of organic pollutants. g-C3N4 is widely used in
recent years due to its physicochemical properties and electronic
band structure (Xu et al., 2015; Mishra et al., 2018). It can be
developed as potential metal free, non toxic photocatalyst with
good response in visible light with suitable band gap of 2.7 eV
(Wang et al., 2010, 2011; Jiang et al., 2017). Additionally, in an
ambient condition it is chemically and thermally stable, having low
density, layered structure, resistivity towards water.
Scheme 1. Steps for the synthesis of g-C3N4/H-ZSM-5 composite.
Biocompatibility originates it greatly promising in the area of
photocatalysis (Mishra et al., 2018). Therefore by synthesizing the
composite of zeolite and g-C3N4 which is visible light active, com-
prises a good photocatalyst for the degradation of dye and pesticide
which takes place in dark till the equilibrium is achieved. Yang et al.
prepared Bi2SiO5/g-C3N4 heterojunctions by a template-free hy-
drothermal method, and this nanocomposite has been used for the
decolorization of crystal violet (CV) in visible-light (Yang et al.,
2016). However, the photocatalytic properties of g-C3N4/H-ZSM-5
composite have not been widely studied thoroughly so far.
In the present study, we are focused on synthesis of g-C3N4/H-
ZSM-5 composite by calcination route and further used for degra-
dation of Methylene Blue (MB) and EDC (Fipronil). The various ef-
fects like catalyst dose, pH and scavengers have been studied.
2. Experimental
2.1. Materials
H-ZSM-5 zeolite and melamine were purchased from Thermo
Fisher Scientific India Pvt. Ltd. and S D Fine-Chem Limited, Indus-
trial Estate, Mumbai respectively. The Methylene Blue (MB) dye was
purchased from Merck and Fipronil was purchased from Bayer Crop
Science Ltd., India. Ultrapure deionized water was obtained from
Millipore (USA, resistance: 18 MU) to prepare the stock solution of
MB and Fipronil (FIP), and also for washing of the glassware.
2.2. Preparation of g-C3N4/H-ZSM-5 composite
About 2.5 g of calcined H-ZSM-5 zeolite was taken along with
2.5 g melamine in 50 ml of distilled water. The mixture of zeolite
and melamine were stirred for 24 h. Then the slurry was allowed to
re-crystallize by drying at 60  C in an oven for 12 h. Then the re-
crystallized material was put in furnace for 2 h (10  C/min ramp)
at 550  C temperature. The light brownish yellow colored powder
was formed after calcination which confirmed the formation of g-
C3N4/H-ZSM-5 composite (Mishra et al., 2018). The scheme for the
synthesis of g-C3N4/H-ZSM-5 composite is shown in Scheme 1.
2.3. Characterization method
The XRD pattern for g-C3N4/H-ZSM-5 was acquired by Pan
Analytical X’Pert-Pro X-ray diffractometer instrument using CuKa
 Aanchal et al. / Chemosphere 241 (2020) 124981
radiation (45 kV, 40 mA and step size 0.013 ) [(l ¼ 1.5406 Å) over a
scanning period (2Ɵ) from 10 to 90 with slow scanning speed i.e.
2 /min. The HRTEM (High-Resolution Transmission Electron Mi-
croscopy) characterization was done by FEI TECHNAI G2 at 200 kV
accelerating voltage. The surface morphology and elemental
composition of g-C3N4/H-ZSM-5 were estimated by using FESEM
and EDS (Hitachi SU 8010 FESEM) which operates at 30 kV. The
surface area, pore volume, mean pore diameter and pore-size dis-
tribution analysis of the sample were done by Bru-
nauereEmmetteTeller (BET) method and BarretteJoynereHalenda
(BJH) method [Microtrac BELSORP MINI-II (Bel, Japan)] at 77 K and
were determined by the adsorption-desorption isotherms of ni-
trogen. The X-ray Photoelectron Microscopy (XPS) technique was
carried out with monochromatic aluminum source (i.e. Al ka ra-
diation) on Omicron ESCA instrument having hn ¼ 1486.7 eV. The
PL emission spectra were recorded by using an instrument of Per-
kinElmer LS-55 spectrofluorophotometer.
2.4. Photocatalytic degradation of methylene blue and Fipronil
About 1 mg of the prepared photo-catalyst g-C3N4/H-ZSM-5 was
poured into the container having 10 mL solution of methylene blue
(MB) dye of concentration 5 mg/L and was irradiated by a visible
light source (Philips CFL lamp) for 120 min after the attainment of
equilibrium. The adsorption equilibrium has been attained in dark
within 40 min. After the photo-degradation experiment, the
treated dye was separated from the catalyst via centrifugation
process. The absorbance value of the treated dye was observed from
UVeVisible spectrophotometer (Specord 205, Analytik Jena, having
a detection limit of 1 ppm) at various time intervals. The distance of
the MB dye from the light source is kept constant for each exper-
iment which was approximately 10 cm. The maximum absorbance
for MB dye was observed at 664 nm (Mishra et al., 2017b). For
Fipronil (FIP) degradation, 1 mg of g-C3N4/H-ZSM-5 was taken in a
50 mL beaker having 25 mL solution (600 mg/L) of FIP and same
procedure was followed. The maximum absorbance for FIP pesti-
cide was observed at 276 nm (Rathi et al., 2019). According to the
Beer Lambert’s law, the concentration is directly proportional to
absorbance value; therefore the degradation efficiency can be
calculated by the formula:

 
 
% Degradation ¼ ðC0  C =C0  100 ¼ ðA0  A =A0  100
(1)
where A0, A and C0, C represents the absorbance and concentration
at time t ¼ 0 and t, respectively. The rate constant of the photo-
degradation experiment was calculated by the equation:
InðC=C0 Þ ¼  kt (2)
where k is the rate constant, C0 and C is the concentration of the
pollutant (dye or pesticide) at time ‘t’ ¼ 0 and t, respectively.
3. Results and discussions
3.1. Adsorbent characterization
3.1.1. BET analysis
The surface area and pore size analysis of g-C3N4, H-ZSM-5 and
g-C3N4/H-ZSM-5 composite were studied by N2 adsorption-
desorption isotherm and BJH (Barrett-Joyner-Halenda) pore size
distribution, shown in Fig. 1(a and b). The BET surface areas of g-
C3N4, H-ZSM-5 and g-C3N4/H-ZSM-5 composite were observed to
be 81, 417 and 172 m2/g, respectively as tabulated in Table 1. This
shows that the composite is having high surface area for the
3
purpose of eliminating the organic pollutants. The g-C3N4 is having
lesser surface area than the composite, so the composite gives
better photocatalytic properties than pristine g-C3N4. The BJH plot
confirms the presence of both micropores and mesopores, which
indicates a good sign for the adsorption as well as for photo-
degradation process.
3.1.2. X- ray diffraction studies (XRD)
The purity and crystallinity of the synthesized g-C3N4/H-ZSM-5
composite were checked by XRD data that is shown in Fig. 1(c). The
2q values at 27.06 and 13.14 were corresponds to (002) and (100)
planes of crystal faces of g-C3N4 (Gogoi et al., 2018), that matched
with the JCPDS card no (JCPDS 87e1526) (Yuan et al., 2016). The
characteristic XRD peaks of H-ZSM-5 zeolite observed at
2q ¼ 13.88 ,14.81,15.8 ,17.69 , 19.26 , 20.75 , 23.16 , 23.90 ,
24.46 , 29.28 , 29.93 , 36.15 , 37.54 , 45.05 and 45.53 , that cor-
responds to diffraction planes of (102), (301), (202), (400), (312),
(113), (332), (303), (133), (352), (630), (800), (352), (10 0 0) and (0
10 0) listed in JCPDS card no 44e0003 (De Rivas et al., 2013).
Availability of both types (g-C3N4 and H-ZSM-5) of peaks in the g-
C3N4/H-ZSM-5 composite confirms that the successful incorpora-
tion of g-C3N4 into crystalline H-ZSM-5 zeolite. The XRD diffraction
pattern of pristine g-C3N4 is shown in Fig. S1. Though, the charac-
teristic peaks of H-ZSM-5 zeolite was not shifted much, confirms
that g-C3N4 does not disturbs the lattice of H-ZSM-5 zeolite
structure.
3.1.3. XPS analysis
The XPS survey spectrum of g-C3N4/H-ZSM-5 composite is
shown in Fig. 1(d). The presence of C and N elements in the com-
posite suggests that incorporation of g-C3N4 into the H-ZSM-5
zeolite structure was successfully taken place (Fig. 1(def)). In high
resolution spectra of carbon (C) 1s, the peak at 284.09 eV corre-
sponds to adventitious carbon C]C (sp2 hybridized) (Mishra et al.,
2018; Bakshi et al., 2007) and the major peak observed at 287.65 eV
assigned to CeNeC and C-(N3) groups in the g-C3N4/H-ZSM-5
composite (Monga and Basu, 2019; Rather et al., 2017). The less
intense peak at 293.47 eV assigned to one of the carbon species
present in tri-s-triazine ring linked to terminal groups like
uncondensed eNH2 (Wang et al., 2015). The high resolution peak of
N 1s was deconvoluted into 3 peaks namely at 398.14 eV for C]
NeC (sp2 hybridized nitrogen) (Li et al., 2015; Cao et al., 2017),
second at 399.71 eV which is due to amino functional moieties
attached with tertiary nitrogen (N-(C3) and CeNeH) (Li et al., 2015)
and the third deconvoluted peak at 403.75 eV which is weak and
assigned to p excitation in g-C3N4/H-ZSM-5 composite due to g-
C3N4 (Li et al., 2016).
3.1.4. EDS and elemental mapping analysis
The EDS analysis in Fig. 2 (a), clearly depicts the peaks of carbon
and nitrogen which are present in g-C3N4. The other elements Si, Al,
Na and O appeared for the H-ZSM-5 zeolite. The results of
elemental mapping in Fig. 2 (b,c) suggest that, there is homoge-
neous distribution of carbon, nitrogen and other elements (Fig S2
(a-d)) for the synthesized g-C3N4/H-ZSM-5 composite.
3.1.5. FESEM and HRTEM studies
The FESEM images (Fig. 3(a) and b) clearly depicts that the
surface of the g-C3N4/H-ZSM-5 composite was not smooth that
means it has irregularity/roughness on the surface of the catalyst
and possess pores like mesopores and micropores. In high resolu-
tion image of the g-C3N4/H-ZSM-5 composite (Fig. 3(b)), it is
observed that there is irregular plate like structures which may
leads to the increased surface area of the catalyst, and further helps
in the elimination of organic pollutants. The HRTEM image
4 Aanchal et al. / Chemosphere 241 (2020) 124981

Fig. 1. (a) N2 adsorption-desorption isotherms, (b) pore size distribution curves, (c) XRD pattern, (d) XPS survey, (e) deconvoluted peaks of Carbon and (f) Nitrogen of g-C3N4/H-
ZSM-5 composite.

Table 1
The comparison of surface area, pore size, and pore volume of H-ZSM-5, g-C3N4 and g-C3N4/H-ZSM-5 composite.

Sample Surface area (m2/g) Mean pore diameter (nm) Micropore volume (cm3/g1) Mesopore volume (cm3/g1)

H-ZSM-5 417 2.57 0.1697 0.1144

g- C3N4 87.6 20.37 0.0045 0.4246
g-C3N4/H-ZSM-5 172 4.25 0.0644 0.1181
 Aanchal et al. / Chemosphere 241 (2020) 124981
Fig. 2. (a) EDS spectrum and SEM micrograph with elemental mappings of (b) Carbon and (c) Nitrogen of the composite g-C3N4/H-ZSM-5.
indicates the layered structure of g-C3N4 with crystalline structure
of the H-ZSM-5 zeolite (Fig. 3(c)).
3.1.6. Optical properties
The photoluminescence (PL) analysis was done by PL emission
spectra used to elaborate the efficacy of charge carrier scavenging,
transfer or separation and for studying the role of photogenerated
electron hole pairs in the g-C3N4/H-ZSM-5 composite and g-C3N4
material. In general, less intense peak of the PL spectra reveals
(lower the recombination rate) longer lifetime and high separation
of photoinduced electrons and holes (Zhang et al., 2016; Ge et al.,
2012; Li et al., 2017). The PL of g-C3N4 and g-C3N4/H-ZSM-5 com-
posite were performed at excitation wavelength of 365 nm as
shown in Fig. 3(e). The g-C3N4/H-ZSM-5 nanocomposite shows its
emission peak at 428 nm which corresponds to green emission
(Prakash et al., 2019). The PL spectra of H-ZSM-5 zeolite indicate
that the observed peak was broad and highly intense at same
excitation wavelength as shown in Fig. S3. The PL intensity of g-
C3N4/H-ZSM-5 composite was much lesser than that of pure g-C3N4
material. It indicates that the H-ZSM-5 zeolite was perfectly
incorporated into the g-C3N4 matrix and the rate of recombination
of electron hole pairs is decreased on the surface of g-C3N4/H-ZSM-
5 composite.
The optical properties like band gap and light absorption range
was examined by diffused reflectance spectroscopy (DRS). In
Fig. 3(f) the excitation absorption peak was observed for g-C3N4/H-
5
ZSM-5 composite at 380 nm. The graph indicates that the com-
posite absorbs light in the visible region (lmax ¼ 400 nm) which
indicates that g-C3N4/H-ZSM-5 composite is visible light active
material. The optical band gap (Eg) was calculated by using the
equation:
 
ðahvÞ1=2 ¼ A hv  Eg
where a represents the absorption coefficient, A is constant, hn
signifies the photon energy and Eg is the optical band gap (Mishra
et al., 2018). The energy gap value of as-synthesized g-C3N4/H-ZSM-
5 composite is shown in Fig. 3(g). The Tauc’s plot suggests that the
band gap of g-C3N4/H-ZSM-5 composite is 2.63 eV (Prakash et al.,
2019).
3.2. Photocatalytic degradation of MB and FIP
To analyze the photo-catalytic behavior of g-C3N4/H-ZSM-5
composite, the photodegradation experiments were carried out
with organic pollutants i.e. MB dye and FIP (EDC pesticide) in
different light source (UV, visible and sunlight). In the photo-
degradation experiment, the initial concentration of MB and FIP
were about 5 mg/L and 600 mg/L, respectively. The time taken for
adsorption-desorption equilibrium of MB and FIP were 40 min and
50 min, respectively in the dark conditions. After attaining
6 Aanchal et al. / Chemosphere 241 (2020) 124981

Fig. 3. (a, b) FESEM images, (c, d) HRTEM images, (e) photoluminescence spectra, (f) UV Visible diffuse reflection spectra, and (g) Tauc plot of as-prepared catalysts.

equilibrium, the experiment was continued for 120e140 min in the
visible light source for the degradation purpose. The degradation
experiment without photo-catalyst was also studied in which the
dye/pesticide was kept under illumination with visible light source
for 120 min/140 min. The absorbance value for both MB and FIP
remains almost constant which indicates that for the degradation
of the dye and pesticide, g-C3N4/H-ZSM-5 photo-catalyst is highly
required (Fig. S4). For comparison purposes, the degradation
experiment of MB and FIP were also carried out in UV light and
sunlight at optimum condition (Fig. S5). The degradation experi-
ments were carried out under direct solar irradiation in the 4th
week of October 2018 and 3rd week of April 2019 for MB and FIP
degradation respectively. The sunlight intensity was measured
with the Pyranometer (LICOR) instrument, USA - Solar radiation
(Watt per square meter) with an average solar flux (~706 W/m2) for
MB and (495e920 W/m2) FIP degradation.
The absorbance value of MB and FIP decreases with increase in
the illuminating time at their corresponding maximum wave-
lengths. The kinetic studies of MB and FIP with g-C3N4/H-ZSM-5
were shown in Fig. 4(aef), which indicates that these pollutants MB
and FIP were almost completely degraded with high rate constants
of 0.00997 and 0.00875 min1 respectively. The rate constant of
pure H-ZSM-5 and g-C3N4 for MB and FIP degradation were given in
Table 2. The degradation efficiency of MB was ~90% and FIP was
~80% at normal room temperature.
3.2.1. Effect of catalyst dose
The effect of catalyst dose on photodegradation was investigated
 Aanchal et al. / Chemosphere 241 (2020) 124981
Fig. 4. Photocatalytic degradation of MB: (a) C/C0, (b) ln C/C0, (c) effect of catalyst dose, and photocatalytic degradation of FIP: (d) C/C0, (e) ln C/C0, (f) effect of catalyst dose.
Table 2
Rate constants for the degradation of MB and FIP.
Sample Light intensity
2
H-ZSM-5 125 W/m
g- C3N4
g-C3N4/H-ZSM-5
to evaluate the optimum amount of the photocatalyst required for
the degradation of organic pollutants. Experiments were carried
out over different catalyst dose such as 0.1, 0.2, 0.3 and 0.4 g/L for
the degradation of MB and 0.04, 0.08, 0.12 and 0.16 g/L of g-C3N4/H-
ZSM-5 composite for degradation of FIP as shown in Fig. 5(a). From
the performed experiments, it has been observed that, on
increasing the concentration of the catalyst the degradation effi-
ciency of the organic pollutants increases. But at higher concen-
tration, some saturation occurred due to the opacity of the solution.
Therefore, the catalyst (g-C3N4/H-ZSM-5) dose i.e. 0.3 g/L for MB
degradation and 0.12 g/L for FIP were optimized.
3.2.2. Effect of pH
The pH is a major factor that controls the photocatalytic
mechanism as it can influence the surface charge of the photo-
catalyst. To study the effect of pH on the photocatalytic degradation
of organic pollutants (MB and FIP) onto g-C3N4/H-ZSM-5 compos-
ite, the degradation experiments were carried out from pH 1 to
11 at 25 ± 2  C. The pH of the organic pollutants (MB and FIP) was
maintained by adding aqueous solution of 0.2 M NaOH and 0.2 M
HCl into the pollutant solutions. From Fig. 5(a), it is observed that,
the degradation efficiency of MB decreases at acidic pH and in-
creases at basic pH however, for FIP, reverse trend was observed
(degradation efficiency was maximum at acidic pH). The maximum
degradation efficiency for MB (~90%) was observed at basic pH (pH
7
Conditions Rate constants
Dose, pH and time MB (min1) FIP (min1)
0.15 g/L, natural pH 7.5, 120 min e MB 0.000088 0.00026
0.06 g/L, natural pH 5.5, 140 min e FIP 0.0034 0.00013
0.00997 0.00875
9) and this phenomenon is well explained by the studies of pHpzc
studies. The pHpzc value for the composite of g-C3N4/H-ZSM-5 is
determined and it was at pH 7.8 (Fig. 5(b)) (Prakash et al., 2019),
which indicates that the surface of g-C3N4/H-ZSM-5 composite can
be negatively charged at pH > pHzpc (i.e., pH > 7.8) and become
positively charged at pH < pHzpc (i.e., pH < 7.8). So at basic pH
(pH > 7.8), there will be an electrostatic attractions between the
negative surface of the photocatalyst and cationic dye, MB (Gürses
et al., 2006). Whereas the maximum photodegradation of FIP
occurred at acidic pH (pH < 7.8), suggests the electrostatic attrac-
tions between the positively surface of the photocatalyst and
anionic pesticide, FIP (Goyal et al., 2016; Xu et al., 2012). Therefore,
for degradation of FIP, pH 4 was optimized and for degradation of
MB pH 9 was optimized.
3.2.3. Reusability and role of illuminating area
The experimental study on reusability of g-C3N4/H-ZSM-5
composite was also performed as one of the major post photo-
degradation issue, which is also necessary to test the stability and
practical application of the photocatalyst. The stability and reus-
ability of g-C3N4/H-ZSM-5 composite were checked for four
consecutive cycles with the photocatalytic degradation of MB. As
shown in Fig. S6, the activity of the photocatalyst was found to be
~70% after 4 cycles which indicate that the catalyst can be reused
for several times and the catalyst is highly stable. The role of
8 Aanchal et al. / Chemosphere 241 (2020) 124981

Fig. 5. (a) effect of pH on MB and FIP degradation, and (b) pHPZC studies by g-C3N4/H-ZSM-5 photocatalyst, (c) effect of illumination area on MB degradation, and (d) effect of
scavengers on MB and FIP degradation.

illuminating surface area for photodegradation of MB was also MB degradation, whereas, for FIP degradation, the addition of
studied under visible light irradiation (Fig. 5(c)). It has been ascorbic acid majorly affects the rate of photodegradation. The
observed that the degradation efficiency increases with increase in attained results suggested that
OH and radical species were
illuminating area, as the area of organic pollutant which has been responsible for the photodegradation mechanism of MB and FIP
exposed to the visible light source is more. The distance of organic organic pollutants, respectively (Mittal et al., 2018; Zhang et al.,
pollutant from visible light source was kept constant i.e. 10 cm away 2018).
from light source, while performing the illuminating area
experiments.
3.2.5. Plausible mechanism for the photocatalytic reaction
The following mechanism may be responsible for the photo-
3.2.4. Scavengers catalytic degradation of the organic pollutants. The mechanism for
To investigate the detailed plausible mechanism of organic the degradation of MB and FIP is described in Scheme 2.
pollutant degradation and to find out the main active species
during photocatalysis, different scavengers were used to quench hv
g  C3 N4 =H  ZSM  5
!g
the corresponding active species. The scavengers used were: .  
ascorbic acid for radicals, DMSO for e radicals and methyl  C3 N4 H  ZSM  5 e ðCBÞ þ hþ ðVBÞ (3)
alcohol for
OH radicals (Wang et al., 2012; Molla et al., 2017; Pelaez
et al., 2016). The concentration of the different scavengers was fixed
at 103 M. As shown in Fig. 5(d), with the presence of g-C3N4/H- (4)
ZSM-5 composite, the addition of MeOH significantly inhibited the

.   .
g  C 3 N4 H  ZSM  5 hþ ðVBÞ þ H2 O / g  C3 N4 H  ZSM  5 þ OH þ Hþ (5)
 Aanchal et al. / Chemosphere 241 (2020) 124981 9

Scheme 2. Photocatalytic degradation mechanism of organic pollutants by g-C3N4/H-ZSM-5 composite.

Table 3
The comparison of different photocatalysts for the degradation of MB and FIP.

Photocatalyst Organic pollutant Catalyst dose & time % degradation Rate constant Reference

ZnS and CdS nanoparticles MB 0.1 g/L, 6 h, 500 W (visible light) 73% 0.00361 min1 Soltani et al., 2012
Hematite (a-Fe2O3) nanoparticle MB 2.5 g/L, 500 min, natural daylight 97% 0.00462 min1 Tan et al., 2013
(Yb, N)eTiO2 MB 3 g/L, 5 h, 30 W (visible light) 93.55% 0.00909 min1 Zhang et al., 2015
g-C3N4@H-ZSM-5 MB 0.3 g/L, 120 min, 45 W (visible light) 92.7% 0.00997 min1 Present work
(Silver-modified Lithium Vanadium FIP 0.5 g/L, 0.5 h, visible light (>400 nm)/sunlight 99.7% e Yin et al., 2015
Phosphate Sphere) ALVPS (500 W)
Fe2O3/TiO2 monoliths FIP 1.5 g/L, 120 min, 45 W (visible light) 88.71% 0.018 min1 Singh et al., 2019
g-C3N4@H-ZSM-5 FIP 0.12 g/L, 140 min, 45 W (visible light) ~89% 0.00875 min1 Present work

pure pristine g-C3N4 which leads to better degradation of the pol-

lutants. Under visible light and sunlight irradiation, the photo-
degradation of MB and FIP by the g-C3N4/H-ZSM-5 composite was
(6) greater than that of g-C3N4 alone. The degradation mechanism was
proposed and discussed in terms of energy band and radicals.

Declaration of competing interest

(7)
The authors don’t have any conflict of interest about the publi-
The comparison study of various photocatalysts in the degra-
cation of the manuscript.
dation of MB and FIP is tabulated in Table 3. From the table, it is
evident that the very small amount of g-C3N4/H-ZSM-5 composite
Acknowledgements
was sufficient to degrade toxic dye and pesticide very efficiently
under visible light irradiation. Therefore, as prepared catalyst can
Ms. Aanchal is thankful to TIET for fellowship and BRNS (Grant
be used as an alternative photocatalyst for the degradation pur-
No: 34/14/63/2014) for BET instrumental facilities. The authors are
poses of toxic pollutants.
also thankful to DST-FIST and Sprint Testing Solutions-Mumbai for
the instrumental services.
4. Conclusion
Appendix A. Supplementary data
The composite of g-C3N4/H-ZSM-5 was successfully synthesized
from Melamine and H-ZSM-5 zeolite. The photocatalytic degrada- Supplementary data to this article can be found online at
tion experiments of MB and FIP were carried out to investigate the https://doi.org/10.1016/j.chemosphere.2019.124981.
activity of the prepared composite. The composite, g-C3N4/H-ZSM-
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