Binary TiO2/RGO photocatalyst for enhanced degradation of phenol

and its application in underground coal gasification wastewater

treatment

Haiyang Fana, b, c, Guiyun Yia, b, c, d , Zhengting Zhanga, b, c, Xiuxiu Zhanga, b, c, Peng Lia, b, c,

Chuanxiang Zhanga, b, c , Lunjian Chena, b, c, Yulong Zhanga, b, c, Qi Suna, b, c

a Henan Key Laboratory of Coal Green Conversion, College of Chemistry and Chemical Engineering,

Henan Polytechnic University, Jiaozuo 454003, China

b Collaborative Innovation Center of Coal Work Safety of Henan Province, Jiaozuo 454003, China

c State Collaborative Innovation Center of Coal Work Safety and Clean-efficiency Utilization, Jiaozuo

454003, China

d Program for Innovative Research Team in the University of Henan Province (211RTSTHN006),

Jiaozuo 454003, China

Abstract

In this work, we synthesize the TiO2/RGO binary nanohybrids through the sol-

anaerobic calcination method, the TiO2 nanoparticles belonging to anatase type were

evenly loaded on RGO surface in the form of Ti-O-C bond. The enhanced

photocatalytic performance can be ascribed to the existence of RGO that can effectively

promote the transfer of photo-induced electron-hole pairs to generate more hydroxyl

radicals (·OH) and superoxide anion (O2·-) degrading phenol. The TiO2/RGO

nanocomposite with weight ratio of RGO to TiO2 (37.0% to 55.7%) has achieved

 Corresponding author. E-mail address: [email protected] (G. Yi).

 Corresponding author. E-mail address: [email protected] (C. Zhang).

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maximum degradation of phenol from aqueous solution, and about 97.87% of phenol

has been removed within 180 min under UV-light illumination. Through GC-MS

tracking of phenol degradation process, it can be observed that long-chain intermediates

will be generated, and these intermediates will eventually be degraded, confirming that

phenol can be completely removed. Additionally, around 67% TOC of simulated

underground coal gasification (UCG) wastewater can be removed after 10 h

degradation using TiO2/RGO binary composites as photocatalysts. All these results

demonstrate that the binary nanohybrids possess great potential for the organic

contaminants destruction from the actual coal chemical wastewater.

Keywords: Binary nanocomposite; sol-anaerobic calcination; photocatalytic

degradation; GC-MS; UCG wastewater; TOC.

1. Introduction

The poisonous organic contamination from various industrial operations and

human activities has gradually turned into an intractable issue in environment

governance, which is harmful to the environment and the living beings.1-3 Among the

various wastewaters, the underground coal gasification (UCG) wastewater mainly

includes phenolic compounds, benzene, a few of polycyclic aromatic hydrocarbons and

heterocyclic compounds.4-6 Among them, phenolic compounds are the most harmful to

human beings.7 Various approaches have been applied to degradation these organic

pollutants, such as adsorption,8 membrane separation,9 chemical precipitation10 and

photocatalytic degradation.11,12 Compared to other strategies, the utilization of

photocatalytic degradation for organic contaminants is currently recognized as one of

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the most promising methods for environmental protection. And the extremely active

free radicals generated by the photocatalytic reaction can degrade organic pollutants

into CO2 and H2O, which will not cause the secondary pollution. Hence, the

development of cost-efficient photocatalysts is gradually becoming a momentous

research hot topic.

Titanium dioxide (TiO2) has been considered as the most valuable photocatalyst

due to its excellent advantages such as nontoxicity, low cost, excellent chemical

stability and outstanding corrosion resistance, compared with ZnO, SnO2, ZrO2, CdS

and other semiconductor materials that have their own losses and toxicity.13-16 However,

the photoinduced electron-hole pairs generated by light-excited TiO2 are extremely to

recombine and the pure TiO2 particles suffer from high aggregation rate, which

decreases its photocatalytic performance, thereby limiting its practical photocatalysis

application.17-19 Therefore, in order to overcome the problems of poor dispersibility and

low photocatalytic activity of pure TiO2 in practical application,20 TiO2 is usually

modified with carbonaceous matrix (graphene,21 carbon nanotubes22 and carbon

dots23,24) to enhance its photocatalytic efficiency.

It is noteworthy that graphene-based nanomaterial can be a promising candidate

for the combination with TiO2 because it can serve as buffer against particles

aggregation and facilitate the transfer of photogenerated electrons and holes.25,26 At

present, there have been research reports on the composite of TiO2 and graphene-based

materials and their application in wastewater purification. For example, Ullah et al.27

used a one-step hydrothermal method to synthesize TiO2-graphene composite for

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methylene blue degradation. They found that the nanomaterial has higher

photocatalytic activity and stability than pure TiO2, the presence of graphene extends

the light absorption range of TiO2 and improve the separation efficiency of

photoinduced electrons and holes. Al-Kandari et al.28 selected graphene oxide (GO) and

TiO2 as raw materials to prepare TiO2/GO nanomaterial by mechanical impregnation

and used it for the photocatalytic degradation of phenol. The results indicated that the

TiO2/GO has high photocatalytic degradation performance for phenol under ultraviolet

light irradiation in the presence of hydrogen peroxide. Haruna et al.29 synthesized The

TiO2-0.25% RGO that exhibited the highest photocatalytic activity for phenol

degradation in aqueous solution and this was attributed to optimal adsorption efficiency

of phenol along with prolonged lifetime of electron-hole pairs, which illustrated that

the TiO2/RGO nanocomposite can be a promising photocatalyst to degrade organic

contaminants better.

Herein, the TiO2/RGO binary nanohybrid would be synthesized by anchoring TiO2

nanoparticles on the RGO nanosheets uniformly via the sol-anaerobic calcination

approach. The photocatalytic property of the TiO2/RGO binary nanocomposite

photocatalysts was for the photocatalytic degradation of a model organic contaminant

phenol in a suspension system, and the nanomaterial was applied for the purification of

coal underground gasification wastewater. Moreover, a convincing photocatalytic

mechanism was proposed and analyzed detailly based on experimental results.

2. Experimental section

Detailed experimental procedures were described in Supporting information.

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Additionally, the fabrication mechanism for TiO2/RGO nanomaterial is illustrated in

Scheme 1.

Scheme 1. Mechanism diagram of the fabrication of TiO2/RGO composites

3. Results and discussion

3.1. Characterization of photocatalyst

The binary TiO2/RGO nanocomposites phase structure was identified by X-ray

diffraction (XRD). As shown in Figure 1, the calcined TiO2 powders possess four peaks

at 25.4°, 37.9°, 48.1°, 55.1° corresponding to the planes of (101), (004), (200) and (211)

of anatase-type TiO2 (JCPDS: 01-071-1167). And there are another peaks appearing at

27.5°, 36.1°, 41.3°, 54.3° and 56.7°, which can be attributed to the diffraction of (110),

(101), (111), (211) and (220) lattice planes of rutile-type TiO2 (JCPDS: 01-073-2224).31

For the TiO2/RGO binary composite synthesized through sol-anaerobic calcination

approach, there are four peaks belonging to the anatase TiO2, which can be assigned as

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(101), (004), (200) and (211) crystal planes. Figure S1 showed the XRD patterns of

TiO2/RGO-H synthesized by hydrothermal method, TiO2-sol and TiO2, it can be

observed that the uncalcined TiO2-sol is in an amorphous state, and the TiO2 in the

TiO2/RGO-H composite is rutile. Compared with rutile-TiO2, the anatase-TiO2 has a

stronger ability to adsorb oxygen, which enables it to capture photoelectrons in the

photocatalytic process, thereby improving the photocatalytic performance of the

photocatalyst.32 Additionally, the XRD pattern of RGO (Figure 1) exhibits a broad

characteristic peak at 25.5° representing the (002) characteristic peak of the graphene

structure,33 while the TiO2/RGO composite does not have the (002) characteristic peak

of graphene, which may be ascribed to the overlap of the characteristic peak of anatase

TiO2 at 25.4°.

Figure 1. XRD patterns of RGO, TiO2, TiO2/RGO-1, 2, 3 and 4 nanocomposites

The morphology features and structure characteristics of TiO2/RGO binary

nanocomposites were investigated by FESEM and HRTEM (Figure 2). As displayed in

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Figure 2a, the SEM image of RGO reveals a gauzy lamellar two-dimensional structure

interlinking with these wrinkles on the edge. The SEM image of the TiO2/RGO

nanohybrid (Figure 2b) displayed that TiO2 nanoparticles are evenly immobilized on

the RGO layers. According to the element mapping image of the binary composite

(Figure 2c-f), it is observed that the C, O and Ti elements are uniformly distributed on

the surface of RGO, confirming the successful load of TiO2 particles in the TiO2/RGO

nanomaterial. In order to further analyze the loading and dispersion of TiO2 on RGO,

TEM characterization of RGO and TiO2/RGO composite materials was performed.

Figure 2g exhibited a transparent tulle-like structure containing obvious curled edges,

which is accordance with the SEM results. In addition, the TEM picture of TiO2/RGO

nanomaterial indicated the RGO nanolayers have been densely covered by TiO2

particles (with a diameter of about 13-15 nm). In addition, the HRTEM image of the

binary TiO2/RGO (Figure 2h) demonstrated the presence of 0.35 nm interlayer spacing

coincides with the (101) lattices spacing of anatase TiO2,34,35 and there are abundant

oxygen holes on the anatase TiO2 (101) crystal surface, which can be used as electron

adsorption centers in the photocatalytic process, thereby efficiently promoting the

photocatalytic reaction of phenol. Moreover, as we can see from the SAED patterns

(Figure 2i), the diffraction rings sequentially correspond to the (101), (004), (200), (211)

and (204) crystal planes of anatase TiO2, which provides further evidence that TiO2

nanoparticles are successfully loaded onto RGO layers without noticeable impurity

formation, corresponding to the XRD analysis.

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Figure 2. SEM images of (a) RGO, (b, c) TiO2/RGO-2 nanocomposites, (d-f) EDS mapping, TEM
and HRTEM images of (g) RGO, (h, i) TiO2/RGO-2 (inset shows the SAED patterns)

Raman spectroscopy was performed to explore the nature of graphitization of as-

prepared samples. As displayed in Figure 3a, the peaks located at 1338 cm-1 and 1600

cm-1 are consistent with the D band (disordered carbon) and G band (graphitic carbon),

which is ascribed to the disordered structure or edge defects and ordered sp2-hybridized

carbon atoms of crystalline graphite, respectively. Meanwhile, a broad peak can be

observed at 2670 cm-1, which indicates the presence of overlapping RGO layers.36 In

addition, according to the Raman spectra of TiO2/RGO nanocomposite, there are four

peaks appearing at 148 cm-1, 396 cm-1, 513 cm-1 and 639 cm-1, which can be assigned

as the vibration peaks of Eg, B1g, A1g and Eg of anatase TiO2.37 The relative intensity

of the disordered D-band and crystalline G-band (ID/IG) that reflects the structural

change information of nanocarbon materials, and a high ID/IG ratio indicates a high

extent of disordered structure. The ID/IG of TiO2/RGO-2 is 0.83, lower than 0.87 of

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RGO, which may be attributed to removal of defect level in TiO2/RGO during removal

of -COOH groups via thermal treatment.29,38 In other words, TiO2/RGO showed a

decrease in ID/IG ratio compared to RGO, demonstrating an increase of the average size

of the in-plane sp2 domains of carbon atoms in TiO2/RGO, resulting from removal of

oxygen containing groups.

Figure 3. (a) Raman spectra of RGO, TiO2 and TiO2/RGO-2; (b) FT-IR spectra of GO, RGO, TiO2
and TiO2/RGO nanohybrids

As shown in Figure 3b, the FT-IR was performed to investigate the chemical

properties of those functional groups belonging to TiO2/RGO, GO and RGO. It can be

observed that, GO has a broad and strong absorption peak near 3429 cm-1 caused by the

-OH stretching vibration in absorbed water, the appearance near 1740 cm-1, 1615 cm-1,

1455 cm-1 and 1135 cm-1 corresponds to the stretching vibration absorption peaks of

C=O, C=C, C-OH and C-O-C respectively, indicating that the GO surface contains

oxygen-containing functional groups such as hydroxyl, carboxyl and epoxy. Compared

with GO, the peak of RGO around 1455 cm-1 is much weaker, but still contains oxygen-

containing functional groups, which confirms that GO is only partially reduced. For

pure TiO2, in addition to the -OH stretching vibration peak at the wavenumber of 3428

cm-1, there is a broad strong absorption peak in the range of 400-880 cm-1 due to the

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stretching of Ti-O-Ti and bending vibration peak.39 As displayed in FT-IR spectra of

TiO2/RGO, except these characteristic peaks similar to GO near 1615 cm-1, 1455 cm-1,

and 1135 cm-1, a broader absorption peak is stronger than pure TiO2 appearing in the

range of 400-945 cm-1, which can be contributed to the stretching vibration of Ti-O-Ti

bond and Ti-O-C bond, preliminarily exhibiting TiO2 and RGO are chemically

bonded.40,41 Moreover, the existence of Ti-O-C bond is beneficial to the formation of

anatase TiO2, thereby enhancing the photocatalytic degradation of phenol.

In order to further analyze the chemical bonds in RGO and TiO2/RGO-2

nanocomposite, the X-ray photoelectron spectra (XPS) was carried out and XPS

spectrum are shown in Figure 4 and Figure S2. From the full spectrum of RGO (Figure

S2a), it can be seen that RGO contains only C and O elements, corresponding to the

characteristic peaks of C1s and O1s at 283.6 eV and 533.5 eV. According to the C1s

high-resolution spectrum of RGO (Figure S2b), the three main peaks centered at 284.7,

285.7 and 288.8 eV can be attributed to C=C/C-C, C-O and C=O bonds, respectively.42

By comparison with RGO, the survey spectra of synthesized TiO2/RGO binary

composite (Figure 4a) confirms the existence of C1s, O1s and Ti2p, which is consistent

with the mentioned XRD results, demonstrating the presence of TiO2 and RGO in the

nanohybrid. As shown in Figure 4b, the high resolution Ti2p spectrum contains two

peaks donated as Ti2p3/2 and Ti2p1/2 at 458.9 and 464.6 eV, which indicates the

presence of Ti (IV) in TiO2/RGO nanocomposite, proving the formation of TiO2.43

Additionally, the high resolution C1s XPS spectra (Figure 4c) can be fitted with three

characteristic peaks appearing at 284.7, 286.2 and 288.6 eV, which can be ascribed to

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the C=C/C-C, C-O-Ti and C=O, further affirming that the RGO was partially reduced.44

The high resolution XPS spectra of O1s of TiO2/RGO-2 (Figure 4d) can be

deconvoluted in three peaks that are 530.3, 531.8 and 533.2 eV, which can be associated

with Ti-O, C-OH and Ti-O-C bonds compared to RGO (Figure S2c). The presence of

Ti-O and Ti-O-C bonds demonstrates the formation of TiO2, confirming the chemical

bonding between TiO2 and RGO.45,34

Figure 4. (a) XPS survey spectrum of TiO2/RGO-2 composite and high-resolution XPS spectra of
(b) Ti 2p, (c) C 1s and (d) O 1s of TiO2/RGO-2

TG-DSC curves of the TiO2/RGO binary nanocomposite are displayed in Figure

S3. It can be seen from Figure S3 that the weight loss of TiO2/RGO nanohybrid is

divided into three stages and the curve of DSC exhibits two major distinct peaks. The first

low-temperature weight loss under 100 ℃ is mainly caused by the desorption of free

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water physically absorbed on the surface, which coincides with the endothermal process

of the DSC curves. In addition, the weight loss from 100 ℃ to 500 ℃ is likely attributed

to the oxidation of oxygen-containing groups on the surface of RGO layers.46 After 450

℃, the TG curves tend to be stable, and the samples hardly lose weight, which reveals

that the prepared binary TiO2/RGO photocatalysts possess high thermal stability.

According to the TG curves, the mass percentages of RGO and TiO2 in the four

TiO2/RGO composite materials can be calculated. The masses of RGO and TiO2 in

TiO2/RGO-1, 2, 3, 4 nanocomposites are 51.0% and 39.0%, 37.0% and 55.7%, 24.0%

and 70.5%, 12.5% and 82.0%, respectively.

The nitrogen adsorption-desorption isotherms and pore size distribution curves of

RGO, TiO2 and four TiO2/RGO nanocomposites are shown in Figure S4 and Figure 5,

respectively. According to the IUPAC classification, the adsorption-desorption

isotherms of RGO (Figure S4a) and the TiO2/RGO nanomaterials (Figure 5a) can be

classified as type IV isotherms with H3 hysteresis loop, which shows comparatively

more open hysteresis loop than pure TiO2 due to the presence of RGO. Moreover, the

pore size distribution calculated from the adsorption branch of the isotherm is presented

Figure S4b and Figure 5b based on BJH method.47 RGO mainly possesses mesopores

distributed in 3-12 nm, while TiO2 contains plentiful microporous (1-2 nm). For the

binary TiO2/RGO materials, the pore size distributions lie within the range of 0.7-12

nm (Fig. 5b) exhibiting the microporous and mesoporous nature, which indicates that

the ratio of RGO and TiO2 plays an important role in affecting the pore structure.

Furthermore, the specific surface area (SSA) and pore structure parameters are

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displayed in Table 1, and the SSA of TiO2/RGO nanocomposites with abundant pores

are obviously higher than pure RGO and TiO2, which is beneficial to facilitate the

transfer and diffusion of adsorbate, thereby enhancing the photocatalytic degradation

efficiency.

Figure 5. (a) N2 adsorption-desorption isotherms and (b) pore size distribution curves
of TiO2/RGO binary composites
Table 1. Pore structure parameters of RGO, TiO2 and TiO2/RGO nanocomposites

Sample SBET (m2 g-1) Vt (m2 g-1) Vmes (m2 g-1) Vmic (m2 g-1) Vmes/Vt (%)
RGO 98 0.055 0.055 0 100
TiO2 81 0.058 0.018 0.04 68.9
TiO2/RGO-1 170 0.170 0.135 0.035 79.4
TiO2/RGO-2 142 0.179 0.155 0.024 86.6
TiO2/RGO-3 135 0.194 0.175 0.019 90.2
TiO2/RGO-4 89 0.201 0.194 0.007 96.5

3.2. Photocatalytic performance evaluation for phenol

Firstly, by preparing different concentrations of phenol and measuring its

absorbance at 270 nm, the standard curve was drawn according to the formula 2:

Abs=0.01411CPhenol+0.01614 (R2=0.9996) (2)

The standard curve and values are listed in Supporting information (Figure S5 and

Table S1). Subsequently, the photocatalytic performance of TiO2/RGO-2 for phenol

was compared with the TiO2/RGO-H materials under natural light and UV-light

irradiation. As shown in Figure S6, whatever under natural light or UV-light, the

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photocatalytic property of TiO2/RGO-2 is higher than that of TiO2/RGO-H, which is

attributed to the existence of anatase TiO2 in TiO2/RGO-2 nanocomposite that can be

more easily excited by light compared with rutile TiO2 in TiO2/RGO-H composite.

Photocatalytic performance of the prepared TiO2/RGO nanohybrids with different

mass ratios of TiO2 to RGO was tested by calculating the removal amount of phenol in

the aqueous solution under ultraviolet light illumination. As displayed in Figure 6a,

about 12% of the original phenol is removed until reaching the adsorption equilibrium

in 30 min under dark condition, which is mainly due to the adsorption effect of RGO.

Moreover, though TiO2/RGO-1 nanomaterial possesses highest SSA, the photocatalytic

removal efficiency of phenol for TiO2/RGO-2 nanocomposite is 97.87%, which is

obviously higher than pure TiO2 (78.25%), TiO2/RGO-1 (93.97%), TiO2/RGO-3

(92.56%) and TiO2/RGO-4 (91.62%). The results indicated the factors that determine

the photocatalytic performance of composite materials are not only the SSA, but also

the mesoporosity. Additionally, the tight inter-combination between RGO and TiO2

particles can facilitate the electron transfer easier, which can meaningfully promote the

carrier separation, thereby enhancing its photocatalytic property. Furthermore, it can be

observed that the binary TiO2/RGO-2 nanocomposite is a promising candidate

photocatalyst for organic pollutants degradation compared with other binary or ternary

photocatalysts, which is displayed in Table S2.

It can be observed from Figure 6b, with the TiO2/RGO-2 photocatalysts dosage

increasing from 10 mg to 50 mg, the photocatalytic degradation rate of phenol is

becoming faster. However, when the dosage is 50 mg, the degradation rate of phenol is

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higher than that of 40 mg before 100 min, and as time goes by, the degradation

efficiency for 40 mg dosage is higher. The reason is that the increase of photocatalyst

will provide more reactive sites initially, which can facilitate the removal efficiency,

while the overmuch photocatalysts may result in the lack of light penetration, thereby

decreasing the degradation rate.48,49 Furthermore, the phenol can be degraded

completely with the dosage of 20-50 mg after 360 min irradiation.

Figure 6. Effect of (a) different samples (TiO2 and TiO2/RGO), (b) photocatalysts dosage, (c)
solution pH (dosage: 40 mg) and (d) initial phenol concentration on photocatalytic degradation of
phenol

According to the previous researches, pH seems to play a significant role in the

photodegradation of numerous organic contaminants.50 pH may influence adsorption

and dissociation of phenol, the surface charge of TiO2, and other physicochemical

properties.51 The real effluent containing phenol can be discharged at various pH, thus

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a series of experiments were carried out to investigate the influence of pH on the

degradation efficiency of phenol by varying the initial pH from 2 to 10 (Figure 6c). The

photocatalytic degradation efficiency of phenol by the TiO2/RGO nanohybrids firstly

increases and then decreases with the increase of pH, demonstrating that phenol

photodegradation over TiO2/RGO was more favorable in acidic condition than alkaline

ones, and the maximum degradation amount of phenol was obtained when pH was 4,

which could be mostly attributed to the interaction/affinity between TiO2 and phenol.

As a solid acid catalyst, TiO2 can induce the photocatalytic degradation reaction owing

to the formation of B and L acid sites.52 Under acidic conditions, the acid sites of TiO2

in the nanocomposites are more possible to play an important role in photodegradation

of pollutants.53 Moreover, based on previous research, the pKa of phenol is 9.98,

illustrating phenol is a weakly acidic compound.54 With the increment of pH, the

proportion of ionic phenol will increase,55 which is not conducive to the adsorption of

pollutants, thereby decreasing the photocatalytic degradation efficiency.

The effect of initial phenol concentrations on the property of photocatalytic

process was evaluated within the range of 10-100 mg L-1. As shown in Figure 6d, when

the photocatalyst dosage is constant (40 mg), with the increment of initial phenol

concentration, the photocatalytic efficiency is gradually decreasing. However, the

phenol with 100 mg L-1 concentration still can be degraded fully after 12 h, which

indicates that the as-synthesized TiO2/RGO photocatalyst by sol-anaerobic calcination

method possesses excellent photocatalytic performance. Interestingly, it could be found

that the degradation rate of phenol seemingly becomes negative, then the

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photodegradation procedure of phenol begins. The time during which concentration is

transparently larger than 100% is recognized as the photoinduction period, and it has

been reported previously in reactions that involve free radicals.29 Additionally, the

apparent concentration increment can be ascribed to desorption of phenoxyl radicals

from the photocatalyst surface and partially stabilized in solution due to free electron

delocalization with the aromatic ring.56,57 Moreover, it was also observed that shortly

after the UV light irradiation, the color of reaction solution appeared darkened, which

can be attributed to the mixture of catechol and hydroquinone in aqueous solution.58

Although peaks ascribed to the ring cleavage and aromatic intermediates as a result of

phenol photodegradation have been reported,59 no obvious maxima which could be

assigned to such phenol photodegradation products were detected, which thereby

further highlight advantages of the TiO2/RGO binary nanohybrids.

3.3. Photocatalytic degradation of simulated UCG wastewater

The total organic carbon (TOC) of water samples is an important basis for

evaluating the degree of organic pollution in wastewater. The 100 mg of TiO2/RGO-2

nanocomposites were put into 200 mL of simulated UCG wastewater with TOC of

67.63 mg L-1, and the TOC content was measured to calculate the removal rate. As

displayed in Figure 7, with the degradation time increasing, the TOC of simulated UCG

wastewater is continuously decomposed. The TOC value can reach 43.09 mg L-1 after

degrading 30 min from the original 67.63 mg L-1, and the removal rate is 36.29%,

exhibiting that the initial stage has a higher degradation rate. Furthermore, the TOC

content is 22.36 mg L-1 after 10 h with a removal rate of 67%, which demonstrates that

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the as-prepared TiO2/RGO nano-photocatalyst can be a promising candidate for the

purification of UCG wastewater.

Figure 7. Photocatalytic degradation of TOC in simulated UCG wastewater by TiO2/RGO-2

nanocomposites

3.3. Catalytic mechanism analysis

Figure 8. Degradation of phenol by TiO2/RGO-2 composite through GC-MS analysis

To further demonstrate the photocatalytic degradation mechanism of phenol by

TiO2/RGO nanocomposite, the GC-MS was performed to analyze the degradation

process of phenol. According to the GC-MS analysis shown in Figure 8, the mass

percentage of phenol quickly dropped from 59.5% to 11.7% within 5 minutes,

meanwhile, the quantity of components in the solution rose sharply from 22 to 30,

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indicating that phenol was rapidly degraded to produce various intermediate products.

At 15 minutes, the content of phenol increased slightly, while the number of

components decreased to 24, illustrating that phenol was continuously degraded and

the intermediate products were further decomposed. The content of phenol has been

reduced to 0 at 30 minutes, however, the components quantity is as high as 38, which

further proves that a variety of intermedium will be generated during the degradation

process of phenol. Although the phenol has disappeared at this time, it does not

represent that phenol has been degraded completely, but converted into a large amount

of intermediate products. Afterwards, the data of 60 min and 120 min displayed that the

intermediate products were gradually degraded, and components number indicated a

downward trend, which further verified the degradation effect of the TiO2/RGO

nanocomposite and preliminarily explained the degradation mechanism. The total ion

chromatograms (TIC) during the degradation of phenol at 5, 30 and 60 min were placed

in Figure S7, Figure 9, and the intermediates and relative contents listed in Table 2,

respectively.

100
Relative abundance (%)

80

60

40

20

0
6 8 10 12 14 16 18 20 22 24 26 28 29
Retention time (min)

Figure 9. The total ion chromatogram (TIC) of phenol degraded under 60 min

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Table 2. The measurement of intermediates by GC-MS during the process of phenol degradation
(the split ratio of GC-MS is 20:1)

Relative amount (wt. %)

Number Component
5 min 30 min 60 min
1 Phenol 83.175 24.085 18.182
2 Dodecane 4.775 2.464 0
3 Tridecane 8.166 4.444 4.025
4 2,6-di-tert-butyl-4-methylphenol 0 1.057 0
5 Diethyl phthalate 3.883 3.15 7.279
6 Tridecanoic acid 0 0 1.136
7 Hexadecanoic acid 0 5.806 17.369
8 2-(((2-ethylhexyl)oxo)carbonyl)benzoic acid 0 0 3.639
(6E, 10E, 14E, 18E)-2, 6, 10, 15, 19, 23-
9 0 58.993 48.37
hexamethl24 carbon-2, 6, 10, 14, 18, 22-hexene

According to the aforementioned results and analysis, a significant photocatalytic

mechanism was proposed, which is exhibited in Figure 10. Under UV-light illumination,

the TiO2 nanoparticles dispersed on RGO sheet were excited to absorb photon energy,

which can facilitate the electrons transfer from the valence band (VB) to conduction

band (CB), correspondingly generating photo-induced electron-hole pairs. Unluckily,

the photogenerated electron-hole pairs can only exist a few nanoseconds, which will

severely induce the recombination of photo-induced electrons (e-) and holes (h+),

thereby decreasing the photocatalytic performance.60,61 Fortunately, the presence of

RGO can provide more transmission channels for electrons, promoting the transfer of

photo-generated electrons from TiO2 CB to RGO surface, which can efficiently reduce

the electron-hole recombination rate, eventually enhancing the photocatalytic property

of the TiO2/RGO binary nanocomposite.62,63 The photogenerated electrons are easily

trapped by the oxygen dissolved in water to generate O2·- due to superior oxidation. In

addition, the photo-induced holes can directly oxidize organic components adsorbed on

the photocatalyst surface or react with adsorbed OH- groups or H2O molecules to

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produce hydroxyl radicals (·OH) who possess the strongest oxidizing ability among the

oxidants present in the water, which can easily oxidize the majority of inorganic and

organic contaminants in wastewater. The photocatalytic degradation mechanism of

phenol can be illustrated by the following equations:60,64

TiO2 + hv ⟶ e- + h+ (3)

TiO2(e-) + RGO ⟶ TiO2 + RGO(e-) (4)

RGO(e-) + O2 ⟶ O2·- + RGO (5)

h+ + H2O ⟶ ·OH + H+ (6)

O2·- + H+ ⟶ ·OH (7)

Phenol + O2·- + ·OH + h+ ⟶ CO2 + H2O (8)

Therefore, the TiO2/RGO binary photocatalyst can be a promising candidate for the

purification of organic wastewater or UCG wastewater.

Figure 10. Photocatalytic mechanism of TiO2/RGO nanocomposites

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4. Conclusion

To sum up, the TiO2/RGO binary nanocomposites were synthesized successfully

by sol-anaerobic calcination approach. The characterization results indicated that the

anatase-type TiO2 particles were uniformly anchored onto RGO nanosheets in the form

of Ti-O-C covalent bond. Under UV-light irradiation, the optimized TiO2/RGO-2

nanohybrid can degrade 97.87% phenol from aqueous solution under weak acid

condition than pure TiO2, which can be attributed to the presence of RGO that can

facilitate the transfer of photogenerated electrons and holes and decrease the

recombination rate of electron-hole pairs to generate more hydroxyl radicals (·OH) and

superoxide anion (O2·-) reacting with phenol. Additionally, according to GC-MS

analysis, long-chain intermediates will be produced during the degradation process of

phenol, but these intermediates will finally be removed, proving that phenol is

completely degraded. Furthermore, the TOC removal rate of simulated underground

coal gasification wastewater can reach 67% after 10 h degradation using TiO2/RGO

binary composites as photocatalysts, which can be a potential candidate for the

purification of actual coal chemical wastewater.

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This work was supported by the National Natural Science Foundation of China

(U1803114), the Education Department Science Foundation of Henan Province

(19A530002, 19A440002), the National Key Research Plan (2018YFB0604500) and

Electronic copy available at: https://ssrn.com/abstract=3844936

the China Postdoctoral Science Foundation (207500).

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