Environmental Research 209 (2022) 112809

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Environmental Research
journal homepage: www.elsevier.com/locate/envres

Construction of SnO2/g-C3N4 an effective nanocomposite for photocatalytic

degradation of amoxicillin and pharmaceutical effluent
Michael raj Sherlin Nivetha a, Jothi Vinoth Kumar a, Jamaan S. Ajarem b, Ahmed A. Allam c,
Velu Manikandan d, Rajaram Arulmozhi a, Natarajan Abirami a, *
a
Department of Chemistry, College of Engineering and Technology, SRM Institute of Science and Technology, Kattankulathur, Tamil Nadu, 603 203, India
b
Zoology Department, College of Science, King Saud University, Riyadh, Saudi Arabia
c
Zoology Department, Faculty of Science, Beni-Suef University, Beni-Suef, Egypt
d
Department of BioNano Technology, Gachon University, 1342 Seongnam-daero, Sujeong-gu, Seongnam-si, Gyeonggi-do, 13120, South Korea

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

Keywords: The current study mainly focused on the fabrication of 2D graphitic carbon nitride-supported tin oxide nano­
Green synthesis particles (SnO2/g-C3N4) for the effective degradation of Amoxicillin (AMX). Tin oxide (SnO2) NPs were prepared
SnO2/g-C3N4 nanocomposite by green and easy modification technique, and then it is decorated over g-C3N4 nanosheets. The structural
Amoxicillin
morphology and surface composition of the synthesized SnO2/g-C3N4 nanocomposite were fully analysed by
Pharmaceutical effluent
Photocatalytic activity.
UV–Vis, XRD, XPS, and HR-SEM with EDAX, FT-IR, and BET analysis. The (HR-TEM) microscopy, the size of
SnO2 NPs which as a diameter is about 6.2 nm. The Raman analysis revealed that the SnO2/g-C3N4 composite
had a moderate graphitic structure, with a measured ID/Ig value of 0.79. The degradation efficiency of antibiotic
pollutant AMX and pharma effluent treatment was monitored by UV spectroscopy. The optical band gap of SnO2
(2.9 eV) and g-C3N4 (2.8 eV) photocatalyst was measured by Tauc plots. To investigate the mechanism through
the photodegradation efficiency of the catalyst was analysed by using different Scavenger EDTA-2Na holes (h+)
has a greater contribution towards the degradation process. Under visible irradiation, SnO2/g-C3N4 nano­
composite has exhibited an excellent degradation performance of 92.1% against AMX and 90.8% for pharma­
ceutical effluent in 80 min.

1. Introduction researchers described that semiconductor-based catalysts are the most

suitable (Singh et al., 2019). Recently, many researchers have done
Water resources are polluted mainly by active pharmaceutical many studies to elaborate highly efficient semiconductor photocatalysts,
components discharged from various pharmaceutical industries like ZnO (de Sousa et al., 2020), TiO2 (Balaraman et al., 2022), CuO
(Mohammad et al., 2019; Ganesan et al., 2020). Most of the industrial (George et al., 2022), CdS (Cheng et al., 2021), NiO, SnO2 (Danish and
wastewater from pharma industries has an extreme level of organic and Muneer, 2021) etc.
inorganic waste and this is because of massive industrial development. In the current scenario, (SnO2) is well-known and suitable for
They are toxic even at low concentrations and harmful to humans and different applications such as biosensors, photocatalysis, electrocatalyst,
living things (Suresh et al., 2020; Khan et al., 2018). Almost 3.2 million and so on. The SnO2 NPs has emerged as an excellent photocatalyst
humans died every year due to contaminated drinkable water. There­ because of its size, corrosion resistance, stability, higher oxidation po­
fore, the elimination of toxic organic molecules from polluted water is tential, economic pricing, chemical inertness, electronic (band gap =
most necessary. The main focus of the study is to degrade the pollutants 3.6 eV), and substantial photochemical stability. The tin oxide (SnO2
from the environmental water system (Aditya et al., 2021). In this type NPs) is an excellent n-type semiconductor photocatalytic processes are
of finding a solution for this problem, the use of photocatalytic oxidation based on the creation of electron–hole pairs by means of through band
approaches has recently become of great interest to the semiconductor gap radiation, so SnO2 nanoparticles are expected to exhibit high pho­
material research field. Photocatalysis is one of the cost efficient and tocatalytic activity owing to large surface areas and optical properties
easiest methods for its total detoxification ability of pollutants, earlier (Kim et al., 2016). SnO2 NPs exhibits different geometrical morphology

* Corresponding author.
E-mail address: [email protected] (N. Abirami).

https://doi.org/10.1016/j.envres.2022.112809
Received 21 December 2021; Received in revised form 21 January 2022; Accepted 22 January 2022
Available online 29 January 2022
0013-9351/© 2022 Published by Elsevier Inc.
M.S. Nivetha et al. Environmental Research 209 (2022) 112809

such as flowers, hollow microspheres, nanoribbons, and spherical par­ laboratory grade (LR) and applied without any pre-treatment.
ticles. The photocatalytic behaviour of SnO2 NPs is spherical shape,
highest crystallinity, best in colloidal stability, higher dispersibility and
2.2. Mimusops elengi leaf extracts (MELE) preparation
larger surface area (Vo et al., 2017; Matussin et al., 2020). The phyto­
chemicals present in the leaf extract of the chosen plant act as remark­
The Mimusops elengi [Family: Sapotaceous] leaves had gathered on
able capping and reducing agents. Plant mediated SnO2 NPs has a lower
the SRM University campus, Kattankulathur, Chennai, India. The
energy gap (2.93 eV) when compared to the widely used TiO2, ZnO and
collected leaves were washed with the DD water by removing the dust
ZrO Nps that were synthesized by chemical means which has a broader
particles and moving to dry the leaves without moister nature for 5–6
band gap around 3.5 eV. The SnO2 NPs layered in the graphitic carbon
days. The dry leaves make into a fine powder using mortar and pestle.
nitride (g-C3N4) sheets it has enhanced in visible-light photocatalytic
10g of the dry leaf fine powder added to the 100 ml DD water, then
process and also act as an excellent electron acceptor because of their
raised in temperature for 40–50 C in 30 min to the extract were getting
◦

high reduction potential (Karmaoui et al., 2018). A mixture of g-C3N4

the dark green colour solution and filtered via Whatman 11 μm filter
nanosheet and SnO2 nanoparticle is a better charge separation, several
paper to eliminate the residual solids and its centrifuged. Finally, the
strategies have to increase the fabricate of SnO2/g-C3N4 nanocomposite
supernatant extract was collected and kept at 5 C and further studies.
◦

(Ji et al., 2017a).

The g-C3N4 is formed in the semi-closed system under the direct
pyrolysis of carbon and nitrogen-containing various organic sources 2.3. Preparation of tin oxide nanoparticles (SnO2 NPs)
such as, melamine (C3H6N6), urea (CH4N2O), ammonium thiocyanate
(NH4SCN), cyanamide (CH2N2), thiourea (CH4N2S) etc. The g-C3N4 is a The green synthesis of SnO2 NPs, 10 ml of MELE was added in 2M
solution of SnCl2.2H2O (40 ml), under continuous stirring 60 C for 2 h.
◦
low-cost, robust, light-responsive polymeric semiconductor material
(Vinoth Kumar et al., 2021; Wang et al., 2018). It has exhibited After that, the colour changed from white cloudy precipitate into brown
considerable attention because of its characteristic layered structure, colour the obtained solid product indicates the formation of tin oxide
very high chemical and thermal stability, non-toxicity, photocatalytic nanoparticles. To remove un-reactant products using double DD water,
ethanol and dried at 70 C for 8 h.
◦
activity, and easy preparation (Xu et al., 2018; Raziq et al., 2020). The
g-C3N4 synthesis of an effective heterojunction and a hybrid semi­
conductor on the photocatalytic system based on various semiconductor 2.4. Synthesis of g-C3N4 nanosheets (g-C3N4)
materials there are g-C3N4/Ag3Po4, g-C3N4/V2O5, g-C3N4/CoTiO3,
g-C3N4/Bi2MoO6, g-C3N4/Bi2O3, g-C3N4/BaTiO3, N-doped The preparation of g-C3N4 nanosheets was prepared earlier reported
g-C3N4/Bi2O3, SnO2/g-C3N4, WO3/g-C3N4, g-C3N4/BiVO4, g-C3N4/V2O5 method, with slight modification carried out one step direct calcination
(Van et al., 2022). The main functional groups –NH2/–NH–/ = N- in the method (Radhakrishnan et al., 2020). 10 g melamine was to be added in
formation, which the binding sites interrelate with heavy metals a crucible and kept in the furnace for calcined at 550 ◦ C in 4 h through
through complexion and redox reaction, and it agrees graphitic carbon the N2-atmosphere, after cooling down the crucible was taken out. A
nitride is a perfect adsorbent to the elimination of heavy metals (Duan bright yellow product is obtained and labelled as g-C3N4 nanosheets.
et al., 2019). Bulk g-C3N4 materials have green synthesis is a suitable
one, which is the simplest and inexpensive method and it can be used for
the production of nanomaterials for a various application that do not 2.5. Fabrication of SnO2/g-C3N4 nanocomposites
need the use of hazardous and expensive chemicals (Jourshabani et al.,
2017). The yellow powder of g-C3N4 nanosheets (1g) and 0.5g of SnO2 NPs
The Mimusops elengi plant leaf extract act as (reducing agent) was were dissolved in 10 ml DD water, and finally a yellowish-brown solu­
chosen novel precursor for the preparation of SnO2 NPs in this study. tion occurred. Then, the obtained colloidal solution was fully dispersed
Plants are mainly used, easily available, biocompatible, low cost and using an ultrasonic bath for 1 h and centrifuged at 6000 rpm. The
harmless to the environment. Plant-based bioactive compounds such as resulting mixture was separated and then washed with ethanol placed in
terpenoids, flavonoids and phenols are responsible for the reducing hot air oven for 7 h at 60 ◦ C. Finally, the prepared SnO2/g-C3N4 nano­
process (Lin et al., 2020; Ebrahimian et al., 2020). composites were ground well and stored for further analysis.
This study aims to synthesize (SnO2/g-C3N4) nanocomposite photo­
catalyst were successfully prepared via green and co-precipitation 2.6. Characterization of synthesized SnO2/g-C3N4 nanocomposite
method. The g-C3N4 exhibits a high porosity, huge surface area,
improved active spices and suitable candidate for photocatalytic The XRD patterns were analysed by a Rigaku X-ray diffract meter
degradation. The synthesized SnO2/g-C3N4 nanocomposite evaluate the (Analytical X’Pert) to find out the crystal structure of the photocatalysts.
photocatalytic process treated by AMX and real pharmaceutical effluent The morphology studies for the prepared SnO2/g-C3N4 nanocomposite
water, under driven visible light irradiation. In the resulting mechanism were done by high-resolution scanning electron microscopy HR-SEM
exposed holes are playing a vital role in degradation. The SnO2/g-C3N4 and HRTEM. The chemical composition of SnO2/g-C3N4 nano­
nanocomposite is used as an excellent photocatalyst for AMX (anti­ composite was studied by an X-ray photoelectron spectrometer (XPS).
biotic) degradation and real pharma effluent treatment. The FT-IR studies were taken by Shimadzu instrument using lab solution
software. UV–vis spectroscopy was analysed on a Jascoinc, at 25 ◦ C and
2. Experimental section the range from 200 to 800 nm. The thermal study was analysed by a
thermogravimetric analyser NETZSCH STA 2500 in the temperature
2.1. Materials and reagents ranges from 0 to 600 ◦ C with nitrogen atm. The photocatalytic perfor­
mance was enhanced by a light source (Xenon lamp, 300 Watts). To find
Tin chloride dihydrate (SnCl2.2H2O, 99.9%), melamine (C3H6N6), the mineralization product, under total organic carbon (TOC) was
ethanol (C2H5OH), HCl (37 wt%), sodium hydroxide (NaOH), amoxi­ studied by the analyser (Mettler Toledo). To check the adsorption-
cillin (C16H19N3O5S), isopropyl alcohol (C3H8O), ethyl­ desorption isotherm, pore size and surface area was calculated using
enediaminetetraacetic acid disodium (C10H18N2Na2O10), and the BET instrument (Autosorb). Mass spectroscopy was studied to
benzoquinone (C6H4O2) was purchased from Sigma-Aldrich, India. Remi analyse the fragments of degradation products of AMX with the Agilent
R–7C Centrifuge (With 6 × 50 ml) machine, Magnetic Stirrer was ac­ LC-MS/Q-TOF using an MS instrument. Raman spectroscopy was ob­
quired from Techno-India. All the reagents and chemicals used were of tained using a Renishaw instrument.

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M.S. Nivetha et al. Environmental Research 209 (2022) 112809

2.7. Degradation of amoxicillin samples were collected and filtered in 11 μm (medium flow filter paper)
in glass bottles, stored in refrigerator further used for treatment. The
The photocatalytic activity of SnO2/g-C3N4 nanocomposites was control experiment conducted in 50 ml pharmaceutical effluent was
assessed by quantifying the degradation of an aqueous solution of AMX treated in the absence of catalyst there is no colour changing. In the
(antibiotic) when exposed to light irradiation (visible) using UV–Vis above effluent solution, 10 mg of the photocatalyst was added in place in
spectrophotometer (Govarthanan et al., 2022). In a photo reactor, a mechanical stirrer (30 min) in dark conditions for adsorption-
visible light was irradiated using 300 W Xe lamp, with a UV cut-off filter desorption should occur in between effluent and SnO2/g-C3N4 nano­
(l > 400 nm). The light travels a distance of nearly 10 cm through the composites. A visible light (300 W Xe lamp) was utilized the reaction
test solution. Throughout the experiment, the temperature of the test mixture was exposed up to 80 min. Further, the standard operating
solution was kept constant by flowing water around jacket. Suspensions procedures (SOP) were used to determine various physicochemical pa­
of the reaction mixture were prepared by adding 10 mg of synthesized rameters like Temperature (T◦ ), Total dissolved solids (TDS- Equonix
SnO2/g-C3N4 nanocomposites to 40 mL of AMX (10 ppm) aqueous so­ meter), Chemical oxygen demand (COD- Digestors), Electrical Conduc­
lutions, respectively. Before starting the photocatalytic reactions, the tivity (EC- Labman), Biochemical Oxygen Demand (BOD- OxiDirect)
reaction mixture was stirred for 30 min under dark to allow equilibrium Sulphates, Chlorides, and Hardness were studied in untreated and
between AMX and nanocomposites. After 30 min, the solution was treated samples (Fouda et al., 2021; Islam and Mostafa, 2020).
irradiated with visible light while the mixture was continuously stirred.
Over an 80 min reaction period, at 20 min intervals, 3.5 mL of the so­ 3. Results and discussion
lution was withdrawn from the reaction vessel. The photodegradation of
AMX (λmax = 228) was analysed using a UV–Vis spectrophotometer 3.1. Optical properties of SnO2/g-C3N4 nanocomposites
(Shimadzu). In the degradation process a trapping experiment were
performed to determine the active species under various radical scav­ The crystalline properties of the prepared SnO2/g-C3N4 nano­
engers in the concentration of 1 mM (IPA), (EDTA-2Na), (BQ). composites were analysed by XRD analysis and as presented in Fig. 1(a).
The sharp and well-defined peaks were found at 26.5◦ , 33.8◦ , 37.9◦ ,
51.8◦ , 54.8◦ , and 57.8◦ , are indexed to (110), (101), (200), (211), (220),
2.8. Pharmaceutical effluent degradation
(002) planes, which is confirmed the presence of SnO2 NPs with earlier
reported literature (JCPDS 41–445) respectively (Mallikarjuna and Kim,
The pharmaceutical effluent is collected from pharma industry
2021; Bhattacharjee et al., 2015). The 2Ɵ values of g-C3N4 appeared at
located in Chennai, Tamil Nadu, and India. The pharma wastewater

Fig. 1. (a) XRD pattern, (b) FT-IR spectra, (c) UV–vis absorption, and (d) band gap values of SnO2, g-C3N4 and SnO2/g-C3N4 nanocomposites.

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M.S. Nivetha et al. Environmental Research 209 (2022) 112809

two sharp and intense peaks at 13.2◦ and 27.3◦ and correspond to observed in the range of 450 nm (Xu and Gao, 2012). The obtained peak
in-plane structural packing of tri-triazine groups, which correspond to represents good intercalation properties and the absorbance band is
(100) and (002) planes (JCPDS 87–1526) (Zhu et al., 2017). XRD results predictable, it depends on several factors, such as bandgap, surface
suggested that the composite of the major diffraction peaks indicated the roughness, impurity and oxygen deficiency. Absorbance peaks display
existence of SnO2 Nps decorated on g-C3N4 sheets (SnO2/g-C3N4) het­ an ultraviolet cut-off around 250–360 nm, this may be the reason for the
erojunction (Kumar et al., 2020). According to our study, the combi­ electrons photo-excitation from the valence band (VB) to the conduction
nation pattern of all assigned diffraction peaks in SnO2 decorated on band (CB) (Gattu et al., 2015). The observed peak exposes that SnO2
g-C3N4 indicated that the novel material shows photocatalytic activity is nanoparticles are a direct bandgap and show absorption spectra because
now more active. when compared with the pure SnO2 NPs owing to the of the electronic transitions occur in VB toward the CB. The energy band
presence of crystalline phase. The FTIR spectrum of SnO2, g-C3N4, and gap (Eg) is determined by Tauc plot relation,
SnO2/g-C3N4 nanocomposites as depicted in Fig. 1(b).
(αhν) ​ = ​ A ​ (hν ​ − ​ Eg) ​ n
Several functional groups were obtained in the prepared materials
within the region of 4000–500 cm− 1. The broad peak detected at where α is the absorption coefficient, Eg is the band gap, hv is the photon
3100–3600 cm− 1 narrates to stretching vibrations of O–H groups pre­ energy and n is a constant that specifies the kind of optical transitions (n
sents on SnO2 NPs surface. The sharp absorption band at 1635 cm− 1 and = 1/2 and 3/2) for allowed and forbidden transitions, respectively.
1400 cm− 1 corresponds to str. vibrations of C–O and C–C functional Fig. 1(d) shows band gap values of SnO2, g-C3N4, and SnO2/g-C3N4
groups present in the g-C3N4. The observed broadband at 1000–1100 nanocomposites evaluation by Tauc plot, the band gap values of SnO2, g-
cm− 1 is correlated to Sn–OH stretching vibrations. In the spectrum of C3N4, and SnO2/g-C3N4 the values are 2.93 eV, 2.88 eV, and 2.82 eV
SnO2 nanoparticles, in 1800 cm− 1 to 850 cm− 1 O–H, C–O, C–C due to respectively (Arya et al., 2018).
organic compounds present in the extract and the strong band at 600 Hence, the lowest bandgap energy of SnO2/g-C3N4 nanocomposites
cm− 1 is assigned to O–Sn–O stretching vibrations which confirms absorbs much in the light irradiation which is helpful for the better
characteristic of SnO2 in the crystalline phase (Shaalan et al., 2016). The photocatalytic efficiency for degradation of AMX and pharmaceutical
absorption peaks at 1230–1625 cm− 1 were display to the stretching effluent.
vibrations of C– – N the large bands at 1230, 1317 and 1397 cm− 1 is the
–
str. vibration of the C–N bond in the aromatic moiety. Additionally,
broadband at 3000–3500 cm− 1 was ascribed to the stretching mode of 3.2. SEM analysis of SnO2/g-C3N4 nanocomposites
uncondensed amine N–H groups in g-C3N4 (Govinda raj et al., 2021).
In Fig. 1(c) optical absorption property of prepared SnO2 is observed The structural morphology and surface properties of the SnO2
by UV–Visible spectroscopy at room temperature (RT) under the range nanoparticles as depicted in Fig. 2 (a). This image indicated the SnO2
of 200–800 nm. The UV region absorption intensity was high and the nanoparticles were spherical in nature and well distributed (Govar­
visible region is low of the SnO2 nanoparticle it is possible for optical thanan et al., 2021). The structural morphology of g-C3N4 shows the
purposes. The black line (SnO2) showed the absorption edge is found to nanosheet of layer structure displayed in Fig. 2(b) (Feng et al., 2018).
be 385 nm, respectively (Mahvelati-Shamsabadi et al., 2021). The red The SEM analysis suggested the SnO2 nanoparticles successfully com­
line (g-C3N4) an absorption peak at 460 nm, and the blue line shows bined to the surface of g-C3N4, were constructed binary nanocomposites
while combining with g-C3N4 was intercalated with SnO2 the peak was (SnO2/g-C3N4) as shown in Fig. 2(c). The elemental composition of
SnO2/g-C3N4 nanocomposites was determined by element mapping

Fig. 2. FE-SEM images of (a) SnO2, (b) g-C3N4, (c) SnO2/g-C3N4 nanocomposite, (d) elemental mapping of Sn, C, O, N.

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M.S. Nivetha et al. Environmental Research 209 (2022) 112809

images as shown in Fig. 2(d). The elemental mapping analysis proved in Fig. 4(b) (Liu et al., 2015). According to the XPS spectrum C 1s, the
that the presence of all essential elements in the SnO2/g-C3N4 nano­ deconvoluted into three peaks get 288.38 eV, 285.57 eV, and 284.60 eV
composites (i.e., Sn, C, O, and N). These results strongly indicate the displayed in Fig. 4(c). The peaks at 288.38 eV correspond to sp2 bonded
catalyst of SnO2/g-C3N4 nanocomposites displays a pearls-like carbon (N–C– – N) and the binding energies at 284.60 eV show that C–C
morphology. coordination of the surface carbon (Tan et al., 2015). The N 1s peak of
g-C3N4 shows two peaks deconvoluted at 398.88 eV, and 400.17 eV, as
depicted in Fig. 4(d). The sharp N1s peak at 398.4 eV represented
3.3. Structural characterization of SnO2/g-C3N4 nanocomposites
sp2-hybridized aromatic N bonded to C atoms (C– – N–C). The peak at
400.7 eV is assigned to the N–H structure (Bao and Chen, 2016). The two
TEM investigations were carried out to understand the microstruc­
strong peaks show sharp peaks at 486.50 (Sn 3d3/2), 494.9 eV (Sn 3d5/2)
ture of the SnO2/g-C3N4 nanocomposites in detail. Fig. 3(a) shows a
in Fig. 4(e), are attributed to Sn4+ ion in SnO2 (Chen et al., 2014). In
TEM image of SnO2 nanoparticles, revealing that the particles have a
Fig. 4(f) shows O1s the main peak at 530.3 eV can be related to the O2−
spherical shape in nature. The layered structure of g-C3N4 shows Fig. 3
ions corresponding to SnO2 nanoparticles and the broad peak at 531.69
(b) it could be found that transforms into the nanosheet morphology
eV corresponds to the H2O, OH− , O2 group presence of absorbed onto
(Srivastava and Mukhopadhyay, 2014; Shen et al., 2019). Fig. 3(c)
the photocatalyst surface a small shift in (binding energy) appears to­
shows a dark black spot highlighted in SnO2 NPs presented on the sheet
wards the lower energies have been found for both Sn and O spectra to
of the g-C3N4. Both SnO2 and g-C3N4 components are bonded to each
the interactions between carbon nitride sheets and tin oxide nano­
other, with SnO2 and g-C3N4 have significant interactions. The SAED
particles (Seza et al., 2018).
patterns of SnO2/g-C3N4 nanocomposites is calculating the diffraction of
ring radius is related with the XRD (JCPDS 41–1445) values, marking
the crystal plane values of (110), and (002) is displayed in Fig. 3(d) (Wu
3.5. Surface properties
et al., 2018). The distinct fringes make evaluation easier of SnO2
nanoparticle in interplanar spacing lattice fringes which are 0.30 nm as
Raman spectra of SnO2/g-C3N4 nanocomposites as displayed in Fig. 5
shown in Fig. 3(e), the anchored SnO2 nanoparticles show a well-defined
(a). The sharp peaks at 630 and 766.47 cm− 1 resemble A1g and B2g
morphology. The obtained nanoparticle size was calculated is 6.2 nm
modes respectively, which is correlated to the asymmetric and sym­
and the range was determined from 1 to 8 nm, and results are displayed
metric stretching of Sn–O bonds. The ’’classical modes’’ confirm the
in (inset: Fig. 3(f)). The sheet of g-C3N4 has an interplanar lattice fringe
tetragonal rutile structure of SnO2 nanostructures compared to XRD
which is 0.33 nm respectively, in Fig. 3(g) corresponding to (002) plane
(Zhao et al., 2015). The spectral analysis of g-C3N4 nanosheets displays
of g-C3N4 it is a good agreement with the XRD pattern (Liu et al., 2016).
characteristic peaks at 630, 708, 766, 1233, 1344, and 1548 cm− 1,
which agrees with the previous literature report. The sharp peak at 1548
3.4. X-ray photoelectron spectroscopy cm− 1similar to the C– – N str. vibration of g-C3N4, it is defined as a
graphitic G band, which represents the formation of a graphite-like
In order to further examine the surface electronic state and elements structure. The peak at 708 cm− 1 indicates the peaks of g-C3N4, is
percentage as-prepared SnO2/g-C3N4 nanocomposites as shown in breathing modes of the s-triazine ring the peaks at 1233 and 1573 cm− 1
Fig. 4. The elemental percentage is given in Fig. 4(a) which suggests that appear owing to the defects or disorder in the graphite structure, as well
the element percentages in, Carbon (C1s), Nitrogen (N1s), tin (Sn3d), as stretching vibration modes of C–– N and C–N heterocycles. The strong
Oxygen (O1s), were C (40.6), N (24.9), O (16.8), Sn (17.7). The full peaks obtained at 1344 and 1548 cm− 1 is represented D and G-bands
survey scan spectrum of the SnO2/g-C3N4 nanocomposites are presented Value was obtained 0.79. The D-band is allotted to the defects and

Fig. 3. TEM images of (a) SnO2, (b) g-C3N4, (c) SnO2/g-C3N4 nanocomposite, (d) Selected area electron diffraction pattern of SnO2/g-C3N4, (e) Lattice fringe (SnO2),
(inset: (f) Particle size of SnO2), (g) lattice fringe g-C3N4 nanosheets.

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M.S. Nivetha et al. Environmental Research 209 (2022) 112809

Fig. 4. XPS spectra (a) elemental percentage (b) XPS full survey spectra of SnO2/g-C3N4 (c) C 1s, (d) N 1s, (e) Sn 3d, (f) O 1s.

Fig. 5. (a) Raman spectra of SnO2/g-C3N4, (b) BET spectra of SnO2/g-C3N4 (inset figure: pore size), and (c) Thermal stability of SnO2/g-C3N4.

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M.S. Nivetha et al. Environmental Research 209 (2022) 112809

disordered atomic arrangements of sp3 hybridized carbon (C) atoms, and m/z 114.45 as shown in Fig. 6(b) above results have been described in
the G-band is graphite carbon vibrations of the C– – C bond (Chaudhary earlier studies (Aksu Demirezen et al., 2019; Kanakaraju et al., 2015).
et al., 2017).
The BET analysis shows the active sites, the surface area of the g- 3.7. Photocatalytic performance of amoxicillin
C3N4 and SnO2/g-C3N4 the nitrogen adsorption and desorption curves
were used to determine the results. The pore size distribution and N2 The photocatalytic degradation of the prepared SnO2/g-C3N4 nano­
adsorption-desorption isotherms of the sample as depicted in Fig. 5(b). composite was investigated in Amoxicillin (absorbance value-227.59
The g-C3N4 material has type IV with H3 hysteresis loops, whereas the nm) under light irradiation (visible) results are displayed in Fig. 7(a).
SnO2/g-C3N4 nanocomposite has type IV with H4 hysteresis loops. The g- The degradation results of AMX using SnO2/g-C3N4 nanocomposite
C3N4 and SnO2/g-C3N4 nanocomposite were 44.7 m2 g− 1 and 65.2 m2 show better photocatalytic performance, with degradation of 92.1%
g− 1, respectively, according to the BET technique the composite mate­ when compared to higher than bare g-C3N4, and SnO2 combination. The
rial is greater than the high surface area of g-C3N4. The SnO2/g-C3N4 bare g-C3N4 is used, it shows less photocatalytic activity owing to the
nanocomposite photocatalyst has a huge surface area, suggesting that inhibitory effect on the interaction between surface plasmon resonance
the rate of photogenerated charge carriers’ recombination has been SnO2 nanoparticles enwrapped on g-C3N4 increased the effective charge
reduced. From the pore size distribution of curves of SnO2/g-C3N4 separation (electron and hole pairs) (Li et al., 2019). All prepared pho­
nanocomposite was much narrow, it was shown that the material had tocatalyst activities are given in Fig. 7(b). The kinetic behaviour and
numerous pore’s structure had the best performance to the reactants/ decomposition rate, of AMX degradation, is denoted by a plot C/C0 Vs
products diffusion and good in transportation during the photochemical time (min) following the reaction pseudo-first-order kinetics is based on
processes. To increase photocatalytic activity, the sample’s high surface the equation:
area is favourable for light absorption, and electron-hole pairs provide a ( )
more active site for the photocatalytic process. The pore size distribution − ln C/C0 ​ = Kt
of g-C3N4, which is 0.16 cm3 g− 1 and the composite of SnO2/g-C3N4
nanocomposite is 0.43 cm3 g− 1 this results revealed a large pore size its where, C is the pollutants of the concentration at time t, C0 is the con­
help from charge separation in the entire composite when parallel to the centration of the initial concentration of AMX, and K is the rate constant
g-C3N4 (Vattikuti et al., 2018; Ji et al., 2017b; Peng et al., 2020). The as given in Fig. 7(c).
thermogravimetric analysis (TGA) was explained in the range of
10–550 ◦ C at the heating ramp rate of 10 ◦ C min− 1 in air atm. It explains 3.8. Pharmaceutical effluent degradation
the thermal stability of SnO2 nanoparticles and SnO2/g-C3N4 nano­
composite as depicted in Fig. 5(c), the SnO2 nanoparticles initial starting Pharmaceutical industry various intermediates to be produced it has
range from 50 to 450 ◦ C the curves indicate the 7% loss and the tem­ a wide range of chemical constituents has a different colour it depends
perature raised to 550 ◦ C only 10% weight loss occurs owing to the upon the drug and various chemical compositions. Over the past decades
volatilization of water content on the sample surface. Another peak the discharge of waste effluent present in pharma industries to our eco-
(black line) indicates the SnO2/g-C3N4 nanocomposite even at 550 ◦ C, system has contributed a potential hazard for both aquatic and terres­
very low decomposition it attributed the functional presented on the trial organisms due to its long shelf life even at low concentrations to
surface, 5% weight loss its mainly converting the carbon nitride mate­ prevent this environmental contamination several technologies were
rials into carbon and nitrogen containing gases and these results adopted in order to degrade this effluents. Even though many conven­
confirmed the SnO2/g-C3N4 nanocomposite great thermally stable (Cao tional techniques such as filtration, biological process, flocculation,
et al., 2017). advanced oxidation process, adsorption etc., has been widely followed,
the photocatalytic degradation seems to be cost efficient, simple and
ecologically benign method. This catalytic degradation using visible
3.6. LC/MS analysis spectra of AMX light gives efficient results in lesser time (Dehghan et al., 2018a). The
absorbance spectra of pharma effluent maximum absorbance peak at
The initial mass value of AMX was obtained before degradation (M = 280 nm as shown in Fig. 8(a). The intensity was decreased using
C16H19N3O5S; molecular weight = 365 g/mol) as shown in Fig. 6(a). SnO2/g-C3N4 nanocomposite and the degradation rate was 90.8% in 80
AMX started with the opening of the four-membered β-lactam ring min of observation in the occurrence of light irritation as compared to
during the degradation process intermediate products formed. The the remaining two materials SnO2 and g-C3N4. All prepared photo­
opening of beta-lactam ring that resulted in protonated amoxicillin catalyst activities are given in Fig. 8(b). In Fig. 8(c) shows the linear
fragmentation after degradation: m/z 314.15, m/z 268.65, m/z 212.90, plots, the R2 values of composite material great response when

Fig. 6. LC/MS analysis spectra of AMX (a) before photocatalytic degradation (b) after photocatalytic degradation.

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M.S. Nivetha et al. Environmental Research 209 (2022) 112809

Fig. 7. (a) UV–visible absorption spectra of AMX degradation over SnO2/g-C3N4, (b) Overall photocatalytic activity of AMX, (c) Kinetic plots.

compared two bare materials. The evidence of the photograph is given in of SnO2 is the main candidate and its responsible for degradation,
Fig. 8(d) for colour decreased initial to final samples (Leelavathi et al., several holes are stored on VB of SnO2 and the sheets of g-C3N4 will
2021). After collecting the degraded final effluents to study the oxidize AMX/pharma effluent. Thus, the CB edge of SnO2 acts as a site
all-physicochemical parameters such as COD, BOD, TDS, EC, pH, tem­ for accepting the excited electrons from the CB of g-C3N4. Photocatalytic
perature, chloride and hardness, and the final results for given in degradation reactions were explained as follows:
(Table 1) comparison between the degradation efficiency of initial and
SnO2 /g − C3 N4 ​ + ​ h→SnO2 /g − C3 N4 ∗
final results reveals the synthesized (SnO2/g-C3N4) effective catalyst for
removal of pharma effluent in 80mins (Racar et al., 2020).
SnO2 /g − C3 N4 ∗ → SnO2 /g − C3 N4 ​ (e− /h+ ) ​ c

3.9. Plausible degradation mechanism SnO2 /g − C3 N4 ​ (e− /h+ )→SnO2 ​ (e− )/g − C3 N4 ​ (h+ )

The possible degradation mechanism for AMX/pharma effluent over e− ​ + ​ O2 →⋅ O2−

SnO2/g-C3N4 photocatalyst was explained as depicted in Fig. 9. The
photocatalytic activity that occurs depends on the size, surface, light
⋅
O2− ​ + ​ 2H+ ​ + ​ 2e− → ​ ⋅ O H ​ + ​ OH−
energy, and quantum efficiency of the photo electron-hole pair. The use
of two semiconducting materials with appropriate band gap (CB and VB) h+ ​ + ​ H2 O→⋅ OH ​ + ​ H+
can be investigated for the simple and rapid separation of photo­
generated carriers, as well as to increase the efficiency of interfacial h+ ​ OH− →⋅ OH
charge transfer. The synthesized SnO2/g-C3N4 nanocomposite photo­ ⋅
catalyst was treated in visible light irradiation a higher charge separa­ O2− ​ + ​ AMX/pharma ​ effluent ​ ​ ​ → ​ ​ oxidant ​ products ​ + ​ H2 O ​ + ​ CO2
tion should (electron-hole pairs) occur. The electrons in the conduction ⋅
O H ​ + ​ AMX/pharma ​ effluent→oxidant ​ products ​ + ​ H2 O ​ + ​ CO2
band of SnO2 recombine with the valence band’s photogenerated holes
of g-C3N4. An excited electron-hole pair should form in the composite of To examine the reactive species involved in the photocatalytic pro­
SnO2/g-C3N4, then the excited electrons in the sheet of g-C3N4 could be cesses of AMX. The experiment conducted the active substance per­
transferred to CB of SnO2 (Saravanan et al., 2021). The photo generated formed in (1 mM) of solution present in ethylene diamine tetra acetic
holes (h+) are formed to be transferred from VB of SnO2 to g-C3N4. The acid (EDTA-2Na), isopropanol (IPA), p-benzoquinone (BQ) were act as
author, Ismael et al., explained by hydroxyl radical (•OH), superoxide trapping agents for the (h+), (•OH), (•O2− ) and dissolved oxygen
radical (•O2− ), and holes (h+) are the reactive species on SnO2 and it is respectively. The above quenchers were added to the degradation
highly responsible for the photocatalytic process and the holes from VB

8
M.S. Nivetha et al. Environmental Research 209 (2022) 112809

Fig. 8. (a) Uv–Visible spectra of pharma effluent degradation over SnO2/g-C3N4, (b) Overall photocatalytic activity (c) kinetic plots, (d) decrease in colour intensity
of pharma effluent. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

Table 1
Testing parameters for un-treated and treated samples.
Various Parameters Units Non-Treated (Before) Treated (After)

pH – 8.3 7.5
EC Ds m− 1 4.36 1.94
T Celsius 30 30
BOD mg L− 1 537.49 111.0
COD mg L− 1 1310.76 284.21
TDS mg L− 1 1268.80 978.11
Chloride mg L− 1 309.73 187.08
Hardness mg L− 1 759.34 326.95

Note: EC-Electrical conductivity, BOD- Biological oxygen demand, COD-

Chemical oxygen demand, TDS-Total Dissolved Solid, T-Temperature.

process and trapping experiments were treated for AMX for photo­
degradation over the activation of SnO2/g-C3N4 nanocomposites. After
the process is completed the photodegradation efficiency of the com­
posite SnO2/g-C3N4 is decreased while added the quencher of EDTA-2Na
it indicating holes (h+). The final process shows that hole (h+) plays a
major role in the AMX degradation process. It can be shown in Fig. 10
(a), adding of BQ (84.79) %, IPA (66.99) %, EDTA (31.96%), and the Fig. 9. Plausible degradation mechanism for AMX by SnO2/g-C3N4
efficiency of AMX 92.1% degradation decreased respectively. These nanocomposite.
results explain in this study the participation of reactive species in AMX
degradation. Finally concluded this study explain h+ was more effective pharma effluent and AMX, respectively, while the degradation efficiency
than (•OH) and (•O2− ) (Balarak et al., 2021). Fig. 10(b) shows the TOC was 92.1% and 90.8% for AMX and pharma effluent under 80 min. The
analysis used to determine the mineralization of pharma effluent and intermediates present throughout the degradation process, which might
AMX using the final photocatalyst. This graph shows that values of be mineralized over a lengthy reaction time period, are responsible for
mineralization efficiency were obtained 37% and 29% were obtained for the variation in mineralization and catalytic efficiency (Bin Chen et al.,

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M.S. Nivetha et al. Environmental Research 209 (2022) 112809

Fig. 10. (a) Effect of radical scavengers on the photocatalytic degradation of AMX over SnO2/g-C3N4 nanocomposite, (b) Mineralization efficiency for AMX of the
final catalyst SnO2/g-C3N4, (c) The reusability of the final Plant@SnO2/g-C3N4 nano catalyst for AMX degradation in successive cycles, and (d) XRD pattern for fresh
and used catalyst.

2017). The reusability and stability of the prepared photocatalyst is irradiation, the synthesized SnO2/g-C3N4 binary catalyst effectively
important key role to evaluate for the final composite. Fig. 10(c) shows decomposed AMX and pharma effluent. Because of the presence of an
the removal percentage of AMX was discovered to be 88.3 percent even excellent heterojunction, effective separation, band structure and light
after four recovery processes, indicating that as-prepared catalyst has a absorption the mesoporous nanocomposites has maximum efficiency
satisfactory reusability potential. It can also be concluded that and improved pollutant removal. This helps to improve the mechanism
SnO2/g-C3N4 was an economical and effective catalyst for AMX removal of the SnO2/g-C3N4 nanocomposites photocatalyst, which was effec­
and to its excellent regeneration performance (Dehghan et al., 2018b). tively elucidated in this work. In 80 min, the degradation efficiency was
Fig. 10 (d) reveals by XRD patterns fresh and used materials reveal the 92.1 percent against AMX and 90.8 percent for pharma effluent. By four
SnO2/g-C3N4 crystalline nature is not destroyed after numerous cycles. cycles of running the XRD data, the exceptional reusability and stability
SnO2/g-C3N4 has a better efficiency than other available catalysts it was of SnO2/g-C3N4 nanocomposites was revealed. The findings of the
compared with earlier literatures as presented in Table 2. trapping tests show that h+ (hole) played the most important role in the
degrading processes. The SnO2/g-C3N4 nanocomposite has an excellent
4. Conclusion degradation potential in AMX and pharma effluent. As a consequence,
the SnO2/g-C3N4 nanocomposite photocatalyst developed might be a
In this work, we used the green approach to make SnO2 nanoparticles remedial material for protecting the environment from pollution.
and adorned them with g-C3N4 nanosheets. Through visible-light
Credit author statement
Table 2
Comparison table for of different catalyst for AMX degradation. Michael raj Sherlin Nivetha: Conceptualization, Data curation,
Manuscript preparation. Jothi Vinoth Kumar: Data curation, Manuscript
Material Technique Time Degradation Reference
(%)
preparation. Jamaam S. Ajarem: Validation, Formal analysis. Ahmed A.
Allam: Data curation, Formal analysis. Velu Manikandan: Validation,
Fly ash UV/H2O2 240 36.1 Ramírez-Franco et al.
Formal analysis. Rajaram Arulmozhi, Formal analysis, Validation.
min (2019)
CuO/ZnO@ photocatalytic 120 79 Darvishi Cheshmeh Natarajan Abirami: Conceptualization, Validation, Formal analysis,
g-C3N4 min Soltani et al. (2018) Supervision.
Magnesium ultrasound 80 84.1 Dehghan et al.
oxide min (2018c)
ZnO@Fe3O4 Sonocatalyst 120 90 Moradi et al. (2021) Declaration of competing interest
min
SnO2/g-C3N4 photocatalyst 80 92.1 Current study The authors declare that they have no known competing financial
min
interests or personal relationships that could have appeared to influence

10
M.S. Nivetha et al. Environmental Research 209 (2022) 112809

the work reported in this paper. factors, reusability and mechanisms. J. Mol. Liq. 264, 98–109. https://doi.org/
10.1016/j.molliq.2018.05.020.
Dehghan, S., Kakavandi, B., Kalantary, R.R., 2018c. Heterogeneous sonocatalytic
Acknowledgment degradation of amoxicillin using ZnO@Fe3O4 magnetic nanocomposite: influential
factors, reusability and mechanisms. J. Mol. Liq. 264, 98–109. https://doi.org/
10.1016/j.molliq.2018.05.020.
The authors wish to acknowledge DST-FIST (S&T) for the Depart­ Duan, J., Zhao, L., Lv, W., Li, Y.J., Zhang, Y., Ai, S., Zhu, L., 2019. Facile synthesis of g-
ment of Chemistry, SRM Institute of Science and Technology (grant no C3N4/Fe3O4 nanocomposites for fluorescent detection and removal of Cr(VI).
SR/FST/CST-266/2015(c)) and Department of Civil engineering SRM Microchem. J. 150, 104105. https://doi.org/10.1016/j.microc.2019.104105.
Ebrahimian, J., Mohsennia, M., Khayatkashani, M., 2020. Photocatalytic-degradation of
Institute of Science and Technology, Kattankulathur. The authors organic dye and removal of heavy metal ions using synthesized SnO2 nanoparticles
acknowledge Researchers Supporting Project number (RSP-2021/149), by Vitex agnus-castus fruit via a green route. Mater. Lett. 263, 127255. https://doi.
King Saud University, Riyadh, Saudi Arabia. org/10.1016/j.matlet.2019.127255.
Feng, J., Zhang, D., Zhou, H., Pi, M., Wang, X., Chen, S., 2018. Coupling P nanostructures
with P-doped g-C3N4 as efficient visible light photocatalysts for H2 evolution and
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