Applied Surface Science 512 (2020) 145629

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Applied Surface Science

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Full Length Article

Ag nanoparticle-impregnated sulfonated graphene/TiO2 composite for the T

photocatalytic removal of organic pollutants
⁎
K. Alamelu, B.M. Jaffar Ali
Bioenergy and Biophotonics Laboratory, Centre for Green Energy Technology, Pondicherry University, RV Nagar, Kalapet, Puducherry 605014, India

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

Keywords: In this study, highly dispersed Ag and TiO2 nanoparticles decorated sulfonated graphene nanosheets (SGTAg)
Sulfonated graphene/TiO2/Ag composite were synthesized and demonstrated to be an efficient photocatalyst for the degradation of aqueous cationic dye
Photocatalysis Rh.B, anionic dye MO and 4-NP under sunlight. Pursuance of photocatalytic degradation of these recalcitrant
4-Nitrophenol organic pollutants over wide pH range shows the catalysts universally degrade all pollutants over 98% in the pH
Methyl Orange
range of 3–7. The reaction kinetics of SGTAg found to be 4–9 fold higher photocatalytic activity than that of
Rhodamine B
pristine TiO2. Analysis of products of photocatalysis by ESI-MS confirms the degradation of Rh.B and MO. Detail
spectroscopic characterization of photocatalyst has been carried out by XRD, UV–vis, PL, FTIR, Raman, FE-SEM,
XPS, and HR-TEM. It is inferred that the enhanced photocatalytic efficiency of nanocomposites in this material
originates from extended light absorption ability in the visible region, effective electron transport ability ren-
dered by Ag loaded sulfonated graphene nanojunction and interfacial electron transfer in the sulfonated gra-
phene nanosheets, as illustrated by UV–Vis and PL emission studies. Further, the results find SGTAg composite to
be highly stable and could be reused for many cycles without significant deterioration of its catalytic activity.

1. Introduction strong oxidizing ability, high photocatalytic activity and tunability of

bandgap [5]. In this direction, to enhance the photocatalytic perfor-
In order to effectively harness sun light for photocatalysis, devel- mance of TiO2, Wang et al., reported Au@rGO/TiO2 composite [6] and
oping efficient visible light active photocatalyst has remained a focus of Pt/TiO2 composite [7] have been studied that can absorb more amount
research for material scientists. The industrial effluent discharge re- of light from the solar spectrum due to surface plasmon resonance and
sulting in recalcitrant organic pollutants contaminating the water exhibits enhancement in the photocatalysis. Wu et al. [8] and Raja et al.
bodies have become a major issue of international concern [1]. Was- [9] have shown that nitrogen doped TiO2 can tune the bandgap of the
tewater from textile, paper, food, leather and other chemical industries material, resulting in absorption of more amount of photons, thereby
containing residual dyes, chlorinated solvents, phenol and aromatic increasing the photocatalytic performance. Kanigaridou et al., reported
compounds are not easily biodegradable [2]. Several methods are being that CuOx/BiVO4 catalyst could degrade bisphenol A dramatically in
followed to remove these organic pollutants from wastewater. In a the presence of bicarbonate [10], Shiamala et al., reported TiO2/
conventional process of wastewater treatment, usually dyes are re- Bi2WO6 heterojunction [11] for degradation of biomass under sunlight,
moved by adsorption or coagulation. However, these methods transfer Limin Hu et al., reported Co3O4-Bi2O3/PMS system exhibits enhanced
dyes from liquid to solid phase, causing secondary pollution unless they degradation of bisphenol A with broad pH range [12], Ajay Rakkesh
are subjected to further treatments [3]. It is therefore quite challenging et al., showed GNS/TiO2/V2O5 core shell structure could absorb more
task to remove highly toxic pollutant found in low concentration in amount of photons from UV and visible region and exhibit enhanced
waste water [4]. Among the several methods adopted for their removal, photocatalytic performance under sunlight [13]. Deepti Chaudhary,
photocatalytic degradation of pollutant constitute a green and cost ef- et al., reported noble metal free C3N4/TiO2/CNT ternary nanocompo-
fective means to address these issues. sites [14] enhanced the photocatalytic performance under visible light.
Semiconductor photocatalyst can degrade recalcitrant compounds Yongfang Yang et al., studied visible light active reduced graphene
in the presence of light. Among various semiconductors, TiO2 and their oxide/meso-TiO2/Au NPs ternary nanocomposite [15] that exhibited
composite are most widely studied system for environmental applica- excellent photocatalytic activity for the degradation of methylene dye.
tion because of their chemical stability, low cost, non-toxic nature, Lijun Luo et al., reported fluorinated TiO2/reduced graphene oxide

⁎
Corresponding author.
E-mail address: jaff[email protected] (B.M. Jaffar Ali).

https://doi.org/10.1016/j.apsusc.2020.145629
Received 11 July 2019; Received in revised form 13 December 2019; Accepted 2 February 2020
Available online 03 February 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
K. Alamelu and B.M. Jaffar Ali Applied Surface Science 512 (2020) 145629

composite exhibiting enhanced photocatalytic activity for the de- 2.3. Photocatalysis experiment
gradation of bisphenol A [16]. In pursuit of cost effective material for
photocatalyst, Ouzzine et al., reported use of activated carbon/TiO2 Separate photocatalytic degradation experiments were performed
[17], N. Zhang et al., reported CdS/graphene/TiO2 hybrids [18] and for the aqueous azo dyes, namely MO (7 ppm), Rh.B (10 ppm) and for 4-
Thomas et al., reported graphene/TiO2 [19] composite all of which nitrophenol (50 ppm). In azo dyes, 0.5 mg/mL photocatalyst was sus-
tune the bandgap of the material and enhance its photocatalytic ac- pended in the aqueous solution and stirred under dark condition for
tivity. These are some of the important directions pursued to enhance 45 min to reach adsorption/desorption equilibrium. Photocatalytic ac-
the photocatalytic performance of TiO2 and utilize more amounts of tivity of the prepared sample was evaluated for the degradation of these
photons from solar spectrum. azo dyes under direct sunlight irradiation. For 4-nitrophenol photo-
In recent years, graphene-based semiconductor photocatalyst has catalytic process, 25 mg photocatalyst, 0.3 mL H2O2 (30 wt%) aqueous
attracted more attention for its potential to address plethora of issues in solution was added into 50 mL of 50 ppm 4- nitrophenol aqueous so-
environmental pollution. Graphene is a two-dimensional carbonaceous lution. Before illumination, the mixed solution was ultrasonically
materials, having high electron mobility, high surface area and also an treated for 10 min and the stirred in dark condition for 60 min to attain
ideal acceptor and transporter for photogenerated electrons [20,21]. adsorption/desorption equilibrium. Then, the mixture was irradiated
Many researchers have reported that graphene/semiconductor compo- under direct sunlight with continuous stirring. 3 mL of sample was
site can improve the photocatalytic performance in terms of high pol- drawn at certain interval, followed by centrifugation to remove the
lutant absorption, reduced the rate of charge carrier recombination, catalyst, the clear solution was monitored by UV–vis spectrometers
increasing the electron transport and also enhanced the light absorption quantify the degradation process. The effects of different concentration
band range [22,23]. To further enhance its properties, noble metal of Ag loading and solution pH (3, 7 and 11) of the photocatalyst on
nanoparticle also have been introduced that significantly improve the organic dye degradation were investigated. All experiments were per-
photocatalytic performance of graphene-TiO2 as well as increase the formed on triplicate samples. Mean value along with its standard de-
light absorption ability in the visible region [24]. This noble metal/ viation were plotted and analyzed. The pH of the dye solution was
composite can restrict the recombination of electron-hole pairs by ef- adjusted by using NaOH or hydrochloric acid. The reactive species re-
ficient transport of photogenerated electron onto the noble metal [25]. sponsible for Rh.B and MO degradation was also identified using the
In this work, to retain the photocatalytic performance of graphene chemical scavenger method. The chemical scavengers namely, p-ben-
and at the same time enhance its stability, sulfonated graphene sheets zoquinone (1 mM), EDTA (1 mM), isopropanol (20 mM), were used to
as an electron transport channel and acceptor has been used. Sulfonated scavenge the O2●-, h+ and ●OH, respectively. The experimental pro-
graphene is a kind of modified graphene with plenty of –SO3H group on cedure for reactive species identification was similar to the photo-
the surface and edge of graphene sheets, which is highly water soluble catalytic degradation experiments except that the chemical scavenger
and excellent charge conductivity. Lot of functional group on the sur- was added before the initiation of the photocatalytic experiment.
face of SGO act as excellent support material for nanomaterial attach-
ments. According to previous report graphene/GO- TiO2 composites 3. Results & discussion
would be destroyed under alkaline condition due to damage of inter-
action between graphene/GO sheets and TiO2 [26]. This deficiency is 3.1. X-ray diffraction studies
overcome in sulfonated graphene which gives added stability and ef-
fectiveness to the catalyst over a wide pH range. We report the process The crystal phases of the synthesized material were characterized by
of increasing the photocatalytic performance and extend the light ab- XRD and given in Supplementary Material. The results of XRD confirms
sorption ability of TiO2 by adopting Ag nanoparticle and graphene the presence of GO and transformation to SGO [30,31]. The XRD pat-
sheets as an electron transport channel and acceptor, which has a sig- tern (Fig. S1.b) of TiO2 reveals the biphasic nature of material com-
nificant bearing on the recombination rate. A detailed investigation on posed of anatase and rutile phase. Analysis of XRD pattern of nano-
the sulfonated graphene/TiO2/Ag ternary composite characterization composites reveal presence of face centered cubic Ag nanoparticles
and photocatalytic performance of the catalyst on recalcitrant organic deposited on nanocomposites [32].
compound is presented.
3.2. Raman spectroscopy analysis
2. Experimental methods
Raman spectroscopy is one of the extensively used characterization
2.1. Materials technique to measure the structural and electronic properties of the
graphene including disorder and defect structure. Fig. 1(a) shows the
Titanium tetra isopropoxide and n-propanol were purchased from Raman spectra of GO and SGO. The peaks approximately at 1352 and
Spectrochem. Graphite flakes, Potassium permanganate, Sodium 1607 cm−1 ascribed to the D and G band of GO. Moreover, the shift in
Nitrate, Sodium hydroxide, Nitric acid, Hydrochloric acid and Sulfuric the D and G band of Raman peak is observed for sulfonated graphene.
acid were purchased from Sisco Research Laboratories (SRL). Ethylene The G band corresponds to sp2 carbon forms and furnishes the in-
glycol, Silver nitrate, Sodium 2-chloroethanesulfonate, Hydrogen per- formation on the in-plane vibration of sp2 bounded carbon atoms, al-
oxide, Rhodamine B, Methyl Orange and 4-nitrophenol were purchased though the D band proposes the presence of sp3 defects. The intensity
from Merck. All the chemicals were used as received. ratio of the D and G band ID/IG, which provides the information on
relative concentration of local defects or disorder compared to the sp2
2.2. Synthesis of photocatalyst hybridized graphene domains [33]. The ID/IG value increased from 0.91
for GO to 1.02 for sulfonated graphene suggests that the sulfonation
TiO2 nanoparticles and graphene oxide were synthesized as re- process has modified the structure of GO and the SG has more amount
ported earlier [27]. Sulfonated graphene oxide nanosheets were pre- of sp3 carbon atoms than in GO. This also means sulfonated graphene
pared following sulfonation reaction as described in the literature [26]. has more defects than GO [27]. Fig. 1 (b) shows the Raman spectra of
The different concentrations of Ag NPs loaded SGT (1 mM, 2 mM, and TiO2, SGT and SGTAg nanocomposites. The ID/IG values of nano-
3 mM, AgNO3 loaded) ternary nanocomposites were prepared by polyol composites are decreased compared to sulfonated graphene oxide, in-
method [28,29]. The detail description of protocol followed for the dicating more graphitization of nanocomposites obtained during hy-
synthesis of all photocatalyst material along with the instruments used drothermal method and as well as confirming the reduction SGO to
is provided in Supplementary Materials. rSGO [34]. Further, the other peaks appeared at 147.3, 401, 520.5,

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K. Alamelu and B.M. Jaffar Ali Applied Surface Science 512 (2020) 145629

Fig. 1. Raman spectra of (a) GO and SGO; (b) TiO2, SGT and Ag impregnated sulfonated graphene/TiO2 Photocatalyst.

638 cm−1 corresponds to Eg, B1g, A1g, Eg of anatase TiO2, and the and 2.46 eV, corresponding to pristine TiO2, SGT, SGTAg1, SGTAg2 and
peak at 444 cm−1 corresponds to Eg of rutile TiO2. The SGT and noble SGTAg3 nanocomposites, respectively. The absorbance of SGT and
metal-doped SGT nanocomposites show both TiO2 peaks and D, G SGTAg composites increases significantly in the visible region com-
bands of graphene, which further confirms the nanocomposites for- paring with pristine TiO2. It was found that with the incorporation
mation. sulfonated graphene oxide, the bandgap energy of TiO2 was tuned to
2.85 eV. The narrowing of bandgap is attributed to the chemical in-
3.3. UV–Vis absorption spectroscopy analysis teraction between TiO2 and SG leading to the formation of Ti-O-C bond,
where the electrons on the surface of TiO2 are bonded with unpaired
Fig. 2a shows the UV–visible absorption spectra of TiO2, SGT and electrons of SG leading to upward shift of valence band edge. Further
SGTAg nanocomposites. TiO2 nanoparticle shows strong absorption in narrowing is exhibited in ternary nanocomposite where loading of Ag
the UV region. The enhanced absorption of SGT and SGTAg nano- result in more absorption than SGT due to SPR effect of AgNPs. The
composites are attributed to the presence of SGO. It is noted that SGT existence of AgNPs on the surface of TiO2 significantly modulates the
nanocomposites exhibit shift in the absorption edge towards visible effective dielectric constant surrounding the matrix, leading to visible
region with the introduction of SGO. Upon Ag loading, SGT nano- light absorption.
composites shows strong absorption at 450 nm, the peak intensity in-
creases with increasing concentration of Ag nanoparticles, which could 3.4. Fourier transform infra-red spectroscopy
be attributed to the effect of surface plasmon resonance of Ag nano-
particles [34]. The enhanced absorption in the entire visible region is FTIR spectrum of SGO, TiO2, SGT, and SGTAg nanocomposites
due to the synergetic effect of Ag nanoparticles, rSGO nanosheets and shown in Fig. 3. In the FTIR spectra, broad bands were observed in the
TiO2. The tauc plot of TiO2, SGT, and SGTAg nanocomposites shown in range of 400–1000 cm−1 for TiO2 and nanocomposites, which can be
Fig. 2b, from this, band gaps are deduced to be 2.97, 2.85, 2.83, 2.64 related to the combination of bending and stretching vibrational modes

Fig. 2. (a) UV–Vis absorption spectra of Graphene oxide, Sulfonated graphene oxide, TiO2, and Ag impregnated sulfonated graphene/TiO2 photocatalyst (b) Tauc
plot of corresponding photocatalyst.

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K. Alamelu and B.M. Jaffar Ali Applied Surface Science 512 (2020) 145629

decay function of time scale τ1, τ2 and τ3 (Fig.S2(b) and Table S1,
Supplementary Material). τ1, τ3 represent fast decay component, re-
lated to the recombination of near-surface free exciton, τ2 is a slow
decay component associated with large voids present in the material
and the recombination of interstitially trapped electrons with the holes
in the metal-doped system [37].
The weighted average life time of SGT composites was deduced and
found to decrease with increasing concentration of Ag nanoparticles.
This result suggests that the presence of Ag nanoparticles on the TiO2
surface and sulfonated graphene provides an additional deactivation
pathway corresponding to the electron transfer from TiO2 to Ag nano-
particles and graphene sheets. The shorter lifetime of SGTAg nano-
composites promote quick separation of photoexcited electrons before
its recombines with holes.
The electron transfer rate constant, kET, was determined from the PL
life time of TiO2 in the presence and in the absence of Ag nanoparticles,
using following expression [38]
1 1
kET = −
τ(SGT ) τ(TiO2) (1)
It is noted that kET increases, with increasing concentration of Ag
nanoparticles. It can be inferred that photoexcited electrons from the
TiO2 are trapped by sulfonated graphene sheets and Ag nanoparticles,
Fig. 3. FTIR spectra of SGO, TiO2, SGT, and Ag impregnated sulfonated gra-
leading to reduced charge carrier recombination. It is attributed to good
phene/TiO2 photocatalyst.
interfacial contact between TiO2, sulfonated graphene and Ag nano-
particles.
of Ti-O-Ti in crystalline TiO2 and Ti-O-C bond vibration [35]. The band
appeared at 1087 cm−1 corresponds to a C-O stretching frequency in 3.7. FESEM studies
the alkoxy or epoxy group. In SGO, SGT and SGTAg sample shows a
peak at 1167 cm−1, assigned to (C-SO3H) sulfonic acid group [36], To understand the surface morphologies of the nanocomposites,
which indicates the sulfonic acid group successfully introduced into the FESEM analysis was performed. Results show dense agglomeration of
SGO sheets. In nanocomposites, the band appeared at 1225 cm−1 cor- TiO2 nanoparticles in the range of 10–30 nm and Ag nanoparticles
responds to epoxide C–O–C or phenolic C–O–H stretching vibrations, could be seen on the FESEM images. EDX analysis confirms the presence
1385 cm−1 band is assigned to (C–O) carboxyl group and the peak at of S, Ag and TiO2 nanoparticles on sulfonated graphene sheets (Fig.
1618 cm−1 is related to (C=C) skeletal vibration bands of rSGO, due to S3.d). It is observed that TiO2 and Ag nanoparticles are extensively
the interactions between rSGO and TiO2. The absorption peak at attached on the surface of sulfonated graphene nanosheets, may be due
3400 cm−1 corresponds to the stretching of the (O–H) hydroxyl group. to the presence of oxygenated functional group distributed on its sur-
face. In order to determine the distribution of TiO2 and Ag nano-
3.5. Steady state photoluminescence particles on the surface of sulfonated graphene nanosheets, FE-SEM
imaging and elemental mapping were performed on SGTAg3 which
PL spectroscopy was carried out to probe the nature of charge reveals Ti, O, C, S, Ag elements are uniformly distributed over the
transfer within the material and recombination rate of photogenerated sulfonated graphene sheets (Fig S3.e, Supplementary Material). The
electrons and holes. The sharp PL intensity directly related to the re- homogeneous distribution of the elements indicates, TiO2 and Ag na-
combination rate of photogenerated electrons and holes. It has been noparticles are well attached to sulfonated graphene sheets.
observed that higher the rate of recombination, higher the PL emission.
Alternatively, a lower PL peak intensity revels that more photoinduced 3.8. X-ray photoelectron spectroscopy
electrons are trapped and stably transferred through the interface [26].
The PL spectra of TiO2, SGT and Ag loaded SGT nanocomposites under XPS is a powerful experimental tool to investigate the interaction
the same condition with an excitation wavelength of 325 nm are given between TiO2, carbon, silver, and identify the chemical states of Ti, O,
in Fig. S2(a) (Supplementary Material). A strong band was observed in and Ag on the surface of the SGTAg3 sample. Fig. 4a shows the full scan
the wavelength of 425 nm, assigned to the excitonic PL peak trapped by spectrum of SGTAg3. It demonstrates the existence of Ti, O, S, C and Ag
the defects of the material. The emission peak at 365 and 398 nm elements in the composite, indicating high purity of the sample. Fig. 4b
corresponds to direct and indirect transition of TiO2 material. It is ob- shows the XPS spectrum of Ti 2p, consisting of double peaks located at a
served that intensity of the PL peak decreased for SGT nanocomposites binding energy of 464.3 and 458.5 eV, which correspond to the Ti2p1/2
due to the trapping of photoexcited electrons by sulfonated graphene and Ti2p3/2 spin-orbital splitting in the Ti4+ chemical state [39]. Fig. 4c
sheets, resulting in reduced rate of recombination. The intensity of gives the spectrum of 3d Ag in SGTAg3 composite. The presence of Ag
ternary nanocomposites further weakened compared to SGT and the nanoparticles was detected at two peaks centered at 367.4 and 373.4,
amount of the loading concentration of Ag increases, competing with which is assigned to Ag 3d5/2 and Ag 3d3/2, respectively which is as-
the pristine TiO2. The suppression of PL peak intensity in the nano- cribed to be metallic Ag. High-resolution XPS spectrum of C 1s has
composites due to the efficient interfacial electron transfer between Ag shown in Fig. 4d. The C1s spectrum can be deconvoluted into three
nanoparticles, sulfonated graphene and TiO2. peaks at binding energies of 284.8, 286.2 and 288.6 eV. The peak at
284.8 eV can be attributed to the sp2 hybridized carbon (C–C), peaks at
3.6. Time resolved photoluminescence spectroscopy 286.2 and 288.6 eV corresponds to hydroxyl carbon (C–OH) or epoxy
(C–O), and carboxyl carbon (C=O) functional groups, respectively.
The time-resolved PL decay profiles of TiO2, SGT and SGTAg na- Also, the peak at 288.6 eV corresponds to carbaneous species that form
nocomposites are recorded and the data is fitted to three exponential the Ti–O–C bond, coordination between carbon and TiO2 in the

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K. Alamelu and B.M. Jaffar Ali Applied Surface Science 512 (2020) 145629

Fig. 4. (a) XPS survey spectrum of SGTAg3 composite and (b-f) High resolution XPS spectra of Ti 2p, Ag 3d, C 1s, S 2p, O 1s from SGTAg3 composite.

composite [40]. Fig. 4e shows the high-resolution spectrum of S 2p, the spectra of SGO sample are also obtained (Fig.S4) Supplementary
binding energy at 168.9 eV are ascribed to C–S groups [41]. This Material. It reveals the presence of C, S and O elements in the system.
confirmed the existence of sulfonic functional groups on the surface of Also from the high resolution XPS spectrum of C, S and O, the C1s
SGTAg3 composite. Fig. 4f shows the high-resolution spectrum of O 1s, spectrum can be deconvoluted into three peaks at binding energies of
the peak at 529.8 and 531.2, corresponds to Ti–O and Ti–OH bond 284.4, 286.1 and 288.2 eV corresponds to sp2 hybridized carbon, epoxy
respectively. The results of XPS analyses provide the strong evidence and carboxyl carbon group, respectively. The high-resolution spectrum
that the interaction between sulfonated graphene sheets, TiO2 and Ag of S 2p, the binding energy at 167.7 and 168.9 eV are ascribed to
nanoparticles of SGTAg3 composite. The full scan and high resolution C–SO3H and C–S groups, respectively [41]. This confirmed the

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K. Alamelu and B.M. Jaffar Ali Applied Surface Science 512 (2020) 145629

Fig. 5. HRTEM images of SGTAg3 composite (a, b) Low resolution images (c, d) High resolution images (e) SAED patteren and (f) HRTEM-EDS image of SGTAg3
composite.

existence of sulfonic functional groups on the surface of SGO sample. that TiO2 and Ag nanoparticles are decorated over the sulfonated gra-
phene sheets supporting material. The size of the TiO2 nanoparticles
varies from 8 to 15 nm. Fig. 5 shows the uniform deposition of Ag
3.9. HR-TEM studies nanoparticles over sulfonated graphene TiO2 composite, the size of the
spherical block spots corresponds to the Ag nanoparticles size varies
The size and morphological nature of the nanocomposite were from 4 to 10 nm. The well-resolved lattice fringes with d-spacing of
analyzed by HR-TEM and presented in Fig. 5(a–d). It is clearly evident

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K. Alamelu and B.M. Jaffar Ali Applied Surface Science 512 (2020) 145629

0.35 nm, 0.19 nm, and 0.24 nm corresponds to the lattice plane of increase. The absorption spectra for the photocatalysis of Rh.B at dif-
(1 0 1), (2 0 0) anatase TiO2 and (1 1 1) plane of face-centered cubic Ag ferent pH condition in the presence of SGTAg3 composite are provided
nanoparticle respectively [42], which further confirms TiO2 and Ag in Fig. 7(a–c). The maximum degradation efficiencies were achieved by
nanoparticles are well crystallized. The SAED pattern (Fig. 5e) con- SGTAg3 photocatalyst for MO, RhB dyes at pH-3 and pH-7, respec-
firmed the crystalline nature of SGTAg3 nanocomposite, based on this tively. It was observed that anionic dye is more sensitive to the pH of
pattern it is inferred that prepared TiO2 nanoparticles consist of anatase dye solution compared to cationic dye. Alkaline condition leads to
and rutile phases and metallic Ag nanoparticle. The lattice planes drastic change in anionic dye adsorption, therefore the degradation rate
(1 0 1), (0 0 4), (2 0 0), (2 1 1), (2 0 4) correspond to anatase phase of is lower. In contrast, Rh.B dye do not exhibit appreciable change in the
TiO2 and the lattice plane (2 0 0) correspond to Ag nanoparticles. adsorption on catalyst surface over a wide pH range. The photo-
Furthermore, the energy dispersive X-ray spectroscopy has also been degradation efficiencies of methyl orange and Rhodamine B dye over a
carried out to find the elemental composition in the materials. TEM- wide pH range are given in Table.1. The measured zeta potential
EDX spectrum (Fig. 5f) confirms the presence of Ti, O, S and Ag ele- (Summarized in Table S3 Supplementary Material) of the photocatalyst
ments in the SGTAg3 nanocomposite. TiO2, SGT, SGTAg3 composite at pHPZC found to be of −5.3, −11.6 and
−17.6, respectively. At lower pH values the pHPZC of the composite
4. Photocatalysis carried with a positive charge, whereas, higher pH values led to the
formation of negative charge on the composite. We believe, preserva-
4.1. Photocatalytic degradation of methyl orange and rhodamine B over tion of surface charge modulation with varying pH in the system has
wide pH range rendered universal ability to degrade both anionic and cationic dyes.
The rates of photocatalytic degradation of the dyes were fitted to a
The photocatalytic performance of the prepared catalysts were pseudo-first order kinetics reaction given in Eq. (4).
studied in terms of degradation of model organic recalcitrant pollu-
C
tants, namely, Rhodamine B and Methyl orange over a wide pH range − ln ⎛ t ⎞ = kt
⎜ ⎟

(3, 7 and 11) in an aqueous solution under natural sunlight irradiation. ⎝ Co ⎠ (3)
The initial concentration of the recalcitrant compound found to de-
where C0 is the initial concentration dye after adsorption, Ct is the
crease with increasing irradiation time in presence of a photocatalyst.
concentration after a time t and k is the apparent rate constant, which
The degradation efficiency of recalcitrant compounds was determined
was deduced from a linear fit to the data as shown in Fig.S5 & Fig. 6.
using following expression,
The rate constants for MO and Rh.B are given in Table 2.
C0 − Ct It is noted that rate constant of SGTAg3 composite for MO dye is 9.5,
\% degradation = × 100
C0 (2) 3.0, 1.3 fold and Rh.B dye is 1.5, 3.5, and 1.8 fold higher than that of
pristine TiO2 at pH 3, 7 and 11 respectively. After the introduction of
where C0 is the initial concentration and Ct is the concentration of re-
Ag nanoparticles into sulfonated graphene/TiO2 composite, the pho-
calcitrant compound after irradiation time t. The initial pH of the re-
tocatalytic degradation of the recalcitrant compound progress rapidly,
calcitrant compound plays an important role in its photocatalytic
which is attributed to excited electrons are being effectively transferred
properties, which is not only determine the charges of organic pollutant
into sulfonated graphene sheets by the interaction of Ag nanoparticles
and the photocatalyst material, but also influences the hydroxyl radical
promoted charge carrier separation, inhibiting the electron-hole pair
formation and the aggregation of photocatalysts [43,44]. The adsorp-
recombination. The electrons and holes participate in reduction and
tion capacity of various photocatalyst for MO and Rh.B was obtained
oxidation reaction for the degradation of organic dyes. Moreover, with
(Table S2). The results indicate the degradation rates of Methyl Orange
the introduction Ag nanoparticle into the SGT composite more electrons
and Rhodamine B were dependent on the initial pH of the dye solution.
and holes are generated which can efficiently participate in the re-
The photocatalytic performances of the samples identified from the
duction/oxidation process, and thus improved photocatalytic pursu-
degradation of anionic dye (MO) with a wide pH range under sunlight
ance resulted.
irradiation was also investigated (Fig. S5, Supplementary Material).
The absorption spectra of Methyl Orange photocatalysis over
varying pH condition by SGTAg3 composite have been obtained 4.2. Analysis of intermediate formation (ESI-MS)
(Fig.S6(a–c), Supplementary Material). It has been observed that the
rate of degradation of MO showed maximum at pH-3 and decreased The Rh.B and MO dye were stable in the absence of a catalyst under
with increasing pH. Under acidic pH condition the catalyst surface will irradiation. The reaction process leading to the degradation of Rh.B is
bear a positive charge, therefore it can adsorb more amount anionic discerned from the analysis of ESI-MS performed to identify the for-
dyes and hence undergo fast degradation [41]. Also, the surface charge mation of intermediates products during the degradation process (Fig. 8
of Ag renders Ag loaded composite to be more positive compared to the (a)). As reported in the literature, N-de-ethylation process may be
binary and pure material. The dye adsorption capacity of Ag loaded taking place during the destruction of Rh.B dye chromophore structure.
composite found to be very high at acidic pH. Further, with the increase The photogenerated reactive species such as hole and hydroxide radical
in the pH of dye solution the adsorption decreases. This may be due to could attack the central carbon of Rh.B to decolorize the dye and fur-
the reversal of catalyst surface charges at the negative end for basic pH, ther degrade the molecule via the N-de-ethylation process. From the
consequently, lesser amount of anionic dye is adsorbed. mass spectra, the main intermediate with m/z value of 443, 428, 415
Fig. 6 exhibits the photocatalytic pursuance of the samples mon- and 383 are identified to be N-de-ethylated intermediates of Rh.B
itored by the degradation of cationic dye (Rh.B) over a wide pH range generated following oxidation mechanism (Fig. 8(b)). The m/z 383 has
under sunlight irradiation. Rh.B is a cationic dye and its adsorption been further mineralized into smaller molecular mass fragments viz. m/
behavior in general, contrary to that of anionic dye MO. The catalyst z 301, m/z 296, m/z 297 and m/z 264. It is noted that the major peak of
surface will be positive for acidic pH, therefore the adsorption capacity Rh.B m/z 443 has fully vanished when irradiated over 60 min. The
of dye is less for cationic dye. By increasing the pH of dye solution the obtained intermediates are further degraded into 2-methyl-1-naphthoic
amount of dye adsorption on catalyst surface can increase due to acid (m/z 186), 3,5-dihydroxy-2-(iminomethyl)benzoic acid (m/z 181),
change in surface charge of the photocatalyst. 2-ethylbenzoic acid (m/z 150), 3-methylbenzoic acid (m/z 136), ben-
The results showed that the rate of degradation of Rh.B for SGTAg zoic acid (m/z 122), o- cresol (m/z 108)[43]. Thus it confirms that upon
photocatalyst is maximum at pH-7. By increasing the loading of Ag photocatalysis, the initial Rh.B dye is mineralized to form the inter-
nanoparticles onto SGT composite, the discoloration efficiency found to mediates of smaller molecular mass. The possible structure of the

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K. Alamelu and B.M. Jaffar Ali Applied Surface Science 512 (2020) 145629

Fig. 6. Rate of removal of Rh.B under different photocatalyst (a-c), and corresponding reaction rate constant versus reaction time (d-f) under sunlight at different pH
conditions.

products formed during the photocatalytic degradation of Rh.B is pre- experiments were conducted over wide pH range of 3–10 (Fig. 9). The
sented in Fig.(8.b). In order to understand the degradation reaction absorption spectra for the photocatalysis of 4-Nitrophenol at different
processes of MO, similar ESI-MS analysis was performed to identify the pH condition by SGTAg3 composite is provided in Fig.S8 (–-c)
intermediates products during the degradation process [45,46] (Fig. S7, (Supplementary Material). The degradation of 4-NP is found to be to
Supplementary Material). maximum at pH-6.5. Further, increasing the amount of Ag nano-
particles loading on SGT composite increases the removal of 4-NP.
4.3. Photocatalysis of 4-Nitrophenol over a wide pH range About 97% removal was achieved for SGTAg3 photocatalyst. The re-
moval efficiency of 4-NP drastically decreased for basic pH from 6.5 to
To evaluate the photocatalytic activity for the removal of 4- NP, 10. This might be due to instability of H2O2 in alkaline solution. It is

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K. Alamelu and B.M. Jaffar Ali Applied Surface Science 512 (2020) 145629

Fig. 7. UV-absorption spectra of Rhodamine.B removal with SGTAg3 photocatalyst under sunlight irradiation at (a) pH-3, (b) pH-7 and (c) pH-11.

Table 1
Efficiency of various composites photocatalyst for the degradation of methyl orange and Rhodamine B under varying pH condition.
Catalyst MO degradation efficiency (%) Rh.B degradation efficiency (%)

pH-3 pH-7 pH-11 pH-3 pH-7 pH-11

15 min 90 min 120 min 60 min 60 min 80 min

TiO2 30.5 ± 2.1 74.6 ± 0.8 45.0 ± 0.3 87.3 ± 0.5 71.2 ± 1.0 86.7 ± 0.1
SGT 40.5 ± 0.8 68.0 ± 0.9 47.8 ± 0.1 94.6 ± 0.4 79.6 ± 0.9 77.3 ± 0.7
SGTAg1 97.7 ± 0.1 90.5 ± 0.7 49.0 ± 0.6 87.2 ± 0.6 92.4 ± 0.7 92.7 ± 0.2
SGTAg2 97.8 ± 0.1 95.1 ± 0.1 50.4 ± 0.4 89.7 ± 0.2 94.9 ± 0.8 95.7 ± 0.1
SGTAg3 98.1 ± 0.1 98.5 ± 0.1 56.5 ± 0.5 95.7 ± 0.2 99.2 ± 0.1 97.0 ± 0.1

Table 2
Reaction rate constant for the degradation of methyl orange and Rhodamine B by various composites photocatalyst.
Catalyst Pseudo-first order rate constant of the photocatalytic reaction
kapp (×10−3 min−1)

MO Rh.B

pH-3 pH-7 pH-11 pH-3 pH-7 pH-11

TiO2 23.9 ± 0 0.4 14.9 ± 8.7 5.0 ± 0.2 33.6 ± 0.7 21.2 ± 2.0 24.8 ± 1.2
SGT 29.7 ± 0.4 12.7 ± 0.5 5.2 ± 0.2 46.4 ± 3.6 26.4 ± 1.5 17.8 ± 5.3
SGTAg1 231.4 ± 35.0 24.5 ± 2.8 4.8 ± 0.5 33.2 ± 0.9 42.1 ± 2.8 34.6 ± 1.9
SGTAg2 225.7 ± 39.6 31.0 ± 4.6 5.6 ± 0.4 35.5 ± 1.9 47.1 ± 4.1 42.7 ± 2.6
SGTAg3 237.0 ± 44.1 43.9 ± 6.1 6.6 ± 0.4 50.8 ± 1.8 75.5 ± 3.4 45.5 ± 2.8

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K. Alamelu and B.M. Jaffar Ali Applied Surface Science 512 (2020) 145629

Fig. 8. (a) ESI-MS spectra of Rh.B photocatalyzed by SGTAg3 under sunlight for 0, 30 and 60 min; (b) The proposed photocatalytic degradation pathway for Rh.B.

reported that under alkaline condition, the amount of hydroxyl radical oxidation pathway decided by the catalyst and the pollutant [50]. The
generation is decreased due to presence of more superoxide scavenger schematic representation of energy band diagram and charge transfer
radicals [47]. Table 3 gives the photodegradation efficiency of 4-NP process in SGTAg composite are given in Fig. 10. When the SGTAg
and its rate constant values for a wide pH range. The k for SGTAg3 was sample is irradiated by direct sunlight, the electrons in the valance band
found to be 2 to 4 fold higher than that obtained over the pristine TiO2 of TiO2 are excited to conduction band, leaving holes in the valance
sample at these pH ranges. band. The photogenerated electrons of TiO2 can quickly transfer from
The photocatalytic stability and reusability of the SGTAg3 sample the conduction band to the sulfonated graphene sheets as well as Ag
was also investigated lasting five cycles of photocatalysis under direct nanoparticles [29]. Therefore, efficient charge separation of photo-
sunlight irradiation Fig.S9 (Supplementary Material). The results of generated electron hole pairs is achieved, which is also further con-
SGTAg3 photocatalysis indicate there is no noticeable decrease in the firmed by decreased intensity of PL spectra. The photogenerated elec-
efficiency of photodegradation of MO and Rh.B even after several cy- trons are reacting with oxygen molecules reduced into superoxide anion
cles. radical to react with H+ and electrons to form to hydroxyl radicals. On
In order to evaluate the role of the reactive species (O2●-, h+ and the other hand photogenerated holes are oxidized water molecules to
●
OH) in the photocatalysis, the degradation of MO and Rh.B dyes were produce reactive hydroxide radicals. These radicals are the main active
examined in the presence of various scavengers namely, p-BQ, EDTA- species to facilitate the degradation of recalcitrant compounds. The
Na, and IPA, for different reactive species [48,49], Fig.S10 improved photocatalytic activity on the SGTAg composite could be
(Supplementary Material). Each of the individual scavenger experi- attributed to the synergistic effect of Ag, SGO and TiO2. In addition,
ments were performed separately. The experimental result shows the SGT served as the good supporting material for achieving uniform
addition of EDTA-Na into the photocatalytic system hinder the catalytic distribution of Ag nanoparticles, preventing them from aggregation and
degradation, indicating photogenerated holes are predominantly active thus conserving high photocatalytic performance.
species. For the case of superoxide radicals another reactive species
produced by a simple electron transfer mechanism, p- benzoquinone is
5. Conclusion
used to trap them. This resulted in decrease of photocatalytic de-
gradation efficiency of Rh.B and MO from 99% to 85 and 80% in 90 and
Sulfonated graphene/TiO2/Ag nanocomposites with varying Ag
60 min, respectively. However, with the addition of IPA into the pho-
contents were successfully synthesized via hydrothermal method fol-
tocatalytic system, weak inhibition in the photocatalytic degradation
lowed by polyol process. The incorporation of Ag nanoparticle over SGT
was observed, suggesting that it makes a very small contribution to the
composite was confirmed by XRD, UV–Vis and TEM studies. The ef-
photocatalytic reaction by hydroxyl radical. Based on the above ana-
fective loading of Ag nanoparticles decreased the optical bandgap of
lysis, it is concluded that the degradation of MO and Rh.B is mainly
TiO2 significantly, rendering them suitable for visible light photo-
driven by h+, O2●- species with partial contribution from ●OH species.
catalysis. The SGTAg composite exhibits much better photocatalytic
performance than the TiO2, SGT samples. In that SGTAg3 sample found
4.4. Mechanism of photocatalysis to degrade recalcitrant compound over a wide pH range under sunlight
irradiation. Kinetics study reveals the photocatalytic degradation of
The photocatalytic oxidation of a recalcitrant compound in an recalcitrant compounds obeyed a pseudo-first order reaction me-
aqueous solution follows a superoxide, hole, hydroxyl radicals or mixed chanism. The rate constant of SGTAg3 nanocomposite found to be much

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K. Alamelu and B.M. Jaffar Ali Applied Surface Science 512 (2020) 145629

Fig. 9. Rate of removal of the 4-NP under different photocatalyst (a–c), and corresponding reaction rate constant versus reaction time (d–f) under solar light
irradiation at different pH conditions.

higher than those obtained over SGT and TiO2 samples. We find that in wastewater treatment in real time applications.
sulfonated graphene sheets help increase the electron transport and
reduce the rate of recombination. SGTAg nanocomposite exhibit ex-
cellent photocatalytic activity compared to other photocatalyst which is Declaration of Competing Interest
originated from the synergistic effect between Ag, TiO2 and sulfonated
graphene sheets. We demonstrate that SGTAg composite materials The authors declare that they have no known competing financial
conferred with the capability to efficiently utilize broader spectrum of interests or personal relationships that could have appeared to influ-
solar light could degrade a cationic dye, an anionic dyes and a re- ence the work reported in this paper.
calcitrant compound namely, 4- nitrophenol. This renders it to be a
potential and universal photocatalyst that can be effectively exploited

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K. Alamelu and B.M. Jaffar Ali Applied Surface Science 512 (2020) 145629

Table 3
Efficiency and reaction rate constant for the degradation of 4-NP by various composites photocatalyst.
Catalyst Degradation efficiency (%) Pseudo-first order rate constant of the photocatalytic reaction, kapp (×10−3 min−1)
in 90 min
4-NP 4-NP

pH-3 pH-6.5 pH-10 pH-3 pH-6.5 pH-10

TiO2 62.3 ± 1.3 82.3 ± 0.8 10.2 ± 0.5 10.2 ± 1.8 20.3 ± 3.1 1.1 ± 0.2
SGT 77.2 ± 0.9 86.0 ± 0.1 14.1 ± 0.1 14.8 ± 2.1 21.3 ± 1.4 1.6 ± 0.1
SGTAg1 84.6 ± 0.3 86.1 ± 0.1 17.2 ± 0.6 20.8 ± 2.9 21.1 ± 3.0 1.9 ± 0.2
SGTAg2 90.8 ± 1.1 91.1 ± 1.2 20.9 ± 0.1 25.7 ± 3.4 25.7 ± 2.8 2.6 ± 0.4
SGTAg3 96.9 ± 0.3 97.6 ± 0.5 21.1 ± 0.6 41.1 ± 5.4 40.9 ± 5.6 2.5 ± 0.3

Fig. 10. Schematic illustration of photo-excited electrons and holes transfer among TiO2 NPs, Ag NPs and sulfonated graphene.

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