Open access peer-reviewed chapter

Water Remediation by G-/GO-Based Photocatalysts

Written By

Humaira Seema

Reviewed: 12 February 2019 Published: 23 September 2019

DOI: 10.5772/intechopen.85144

From the Edited Volume

Graphene and Its Derivatives - Synthesis and Applications

Edited by Ishaq Ahmad and Fabian I. Ezema

Chapter metrics overview

776 Chapter Downloads

View Full Metrics

Abstract

Graphene, a two-dimensional sheet of sp2 hybridized carbon atoms, has shown to be the most fascinating and promising option among nanomaterials for a variety of applications, because of its unique structure and tunable physiochemical properties. It can be either in the pure form or in its modified derivatives that include graphene oxide (GO), reduced graphene oxide (rGO), graphene-metal nanoparticle composites, graphene-polymer hybrids, and graphene/organic structures that showed improved results while maintaining inherent properties of the material. These modified nanostructures have a variety of applications as catalysts, energy storage/conversion, antimicrobial, and water decontaminant. In the field of environmental science, graphene has been widely used for molecular sieving involving gas phase separation and organic waste removal from water, due to its biocompatibility, various functional groups, and accessible surface area. Modified graphene can also serve as a semiconductor that can increase the efficiency of the photocatalytic ecosystems that results in the inactivation of the microorganisms causing the organic chemicals to degrade.

Keywords

  • graphene
  • environmental
  • remediation
  • photocatalyst
  • water

1. Introduction

Recently photocatalysis by using semiconductors has fascinated universal consideration for its energy-related and environmental applications. Nevertheless, the decrease in the efficiency of the photocatalysis restricted its practical applications because of the prompt reunion of photogenerated electrons and holes. Thus, to decrease the reunion of charge carriers is significant for improvement of semiconductor photocatalysis. Among numerous approaches, water remediation has been done by rGO-/GO-based materials which are the most favorable candidates due to their high capacity of dye adsorption, prolonged light absorption range, improved separation of charge carriers, and transportation properties leading to improved photoconversion efficiency of the photocatalytic materials [1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74].

1.1 Graphene (rGO)-based photocatalysts

Various numbers of graphene-based photocatalysts have been prepared with its derivatives which mainly comprise metal oxides (e.g., P25 [1, 8], TiO2 [9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 3637], ZnO [17, 39, 40, 41, 42, 43], CuO [44], SnO2 [13, 45], WO3 [46]), metals (e.g., Cu [51], Au [52]), metal-metal oxides (e.g., Ag-TiO2 [35]), upconversion material—P25 (e.g., YF3:Yb3+,Tm3+—TiO2 [38]), salts (e.g., CdS [47, 48, 49], ZnS [50], ZnFe2O4 [53], MnFe2O4 [54], NiFe2O4 [55], CoFe2O4 [56], Bi2WO6 [57, 58, 59], Bi2MoO6 [60], InNbO4 [61], ZnSe [63]), Ag/AgCl [62]), and other carbon material (e.g., CNT [64]).

1.2 Graphene oxide (GO)-based photocatalysts

Graphene oxide (GO) has recently received considerable attention due to oxygen-containing functional groups which increase its solubility in solvents for the preparation of GO-based nanocomposites required for photodegradation of pollutants [65, 66, 67, 68, 69, 70, 71, 72, 73, 74]. GO-based nanocomposites mainly include metal oxides (TiO2) [66, 67, 68, 69, 70, 71, 72], metal-free polymers [73], and silver/silver halides [74].

Advertisement

2. Preparation of rGO-/GO-based composite photocatalysts

Some of the commonly used synthesis techniques include in situ growth strategy, solution mixing, hydrothermal/ solvothermal, and microwave-assisted process.

2.1 In situ growth strategy

This method is usually used to prepare reduced graphene oxide-/graphene oxide-based metal composites. Zhang et al. reported that TiO2/graphene composite photocatalyst [14] is synthesized by a simple liquid-phase deposition technique. Moreover, adopting a similar approach, Wang et al. prepared nanocarbon/TiO2 nanocomposites where titania nanoparticles were decorated by thermal reaction on the surfaces of three different dimensional nanocarbons [9]. While in thermal reduction method, TiO2/graphene composite [12] with a remarkable visible light photocatalytic activity was prepared by Zhang et al. using a heat treatment method of GO, where GO changed to reduced graphene oxide. Uniform ZnO nanoparticles were found on functionalized graphene sheets evenly via thermal decay of mixture of zinc salt, graphene oxide, and poly(vinyl pyrrolidone) [39].

Furthermore, Sn2+ or Ti3+ ions were converted to oxides at low temperatures, while GO was reduced to reduced graphene oxide by tin or titanium salts in redox method [13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45]. In our recent work, we prepared SnO2-G nanocomposite which displayed higher photocatalytic activity in sunlight as compared to bare metal oxide nanoparticles as shown in Figure 1 [45]. Similarly reduced graphene oxide-zinc oxide composite was prepared where zinc ions were decorated on GO sheets and transformed to metal oxide nanoparticles by using chemical reagents at 150°C. Reduced graphene oxide-ZnO photocatalyst is formed by reducing the graphene oxide [43].

Figure 1.

Time-dependent absorption spectra of MB solution during UV light irradiation in the presence of (a) SnO2 and (b) reduced graphene oxide-SnO2 and during sunlight irradiation in the presence of (c) SnO2 and (d) reduced graphene oxide-SnO2. Reprinted with permission of the publisher [45].

Li et al. prepared uniform mesoporous titania nanospheres on reduced graphene oxide layers via a process of a template-free self-assembly [20]. Du et al. [21] also developed the macro-mesoporous titania-reduced graphene oxide composite film by a confinement of a self-assembly process as shown in Figure 2.

Figure 2.

Schematic view for the preparation of a macro-mesoporous TiO2-reduced graphene oxide composite film. Reprinted with permission of the publisher [21].

Moreover Kim et al. synthesized strongly coupled nanocomposites of layered titanate and graphene by electrostatically derived self-assembly between negatively charged G nanosheets and positively charged TiO2 nanosols, followed by a phase transition of the anatase TiO2 component into layered titanate [37]. Chen et al. prepared graphene oxide/titania composites by using the self-assembly technique [72].

While Cu ion-modified reduced graphene oxide [51] prepared by an immersion technique displayed a high photocatalytic activity, gold nanoparticles were decorated on the surface of the reduced graphene oxide through spontaneous chemical reduction of HAuCl4 by GOR [52] as shown in Figure 3.

Figure 3.

Possible mechanism of photosensitized degradation of dyes over a rGO Cu composite under visible light irradiation. Reprinted with permission of the publisher [52].

Bi2WO6/reduced graphene oxide photocatalysts were successfully prepared via in situ refluxing method in the presence of GO [57]. Zhang et al. presented reduced graphene oxide sheet grafted Ag@AgCl plasmonic photocatalyst with high activity via a precipitation reaction followed by reduction [62]. TiO2-GO was well prepared at 80°C by using GO and titanium sulfate as precursors [66].

Liu et al. have established a process of water/toluene two-phase for self-assembling TiO2 nanorods on graphene oxide [69, 70]. Jiang et al. prepared GO/titania composite by in situ depositing titania on GO through liquid-phase deposition, followed by a calcination at 200°C [71].

GO nanostructures are prepared by modified Hummer’s method, which has promising applications in photocatalysis [65].

2.2 Solution mixing method

It has been widely used to prepare graphene-based photocatalysts. Previously, titania nanoparticles and GO colloids have been mixed by ultrasonication followed by ultraviolet (UV)-assisted photocatalytic reduction of GO to yield graphene-titania nanocomposites [18, 23, 31].

Akhavan and Ghaderi used a similar strategy to prepare the titania/reduced graphene oxide composite thin film [25].

Guo et al. [28] prepared TiO2/graphene composite via sonochemical method. GO/g-C3N4 with efficient photocatalytic capability was also fabricated by the same sonochemical approach [73].

ZnO and GO mixture was dispersed by ultrasonication followed by chemical reduction of GO to graphene ultimately leading to synthesize ZnO/graphene composite [40]. The G-hierarchical ZnO hollow sphere composites are synthesized by Luo et al. by using a simple ultrasonic treatment of the solution [43].

Cheng et al. [40] presented a new facile ultrasonic approach to prepare graphene quantum dots (GQDs), which exhibited photoluminescent in a water solution. The water/oil system is used by Zhu et al. [74] to produce graphene oxide enwrapped Ag/AgX (X = Br, Cl) composites. Graphene oxide and silver nitrate solution were added to chloroform solution of surfactants stirring condition at room temperature to produce hybrid composites which displayed high photocatalytic activity under visible light irradiation as shown in Figure 4. Titania/graphene oxide composites were synthesized using one-step colloidal blending method [68].

Figure 4.

(A) Photocatalytic activities of silver/silver bromide (a) and silver/silver bromide/GO (b) nanospecies for photodegradation of MO molecules under visible light irradiation and (B) those of the Ag/AgCl (a) and Ag/AgCl/GO (b) nanospecies. Reprinted with permission of the publisher [74].

2.3 Hydrothermal/solvothermal method

This one-pot process can lead to highly crystalline nanostructures, which operates at elevated temperatures in an autoclave to generate high pressure, without calcination, and at the same time GO reduced to rGO. Typically, graphene-based composites, e.g., P25 [1, 8], TiO2 [15, 16, 24, 29, 30, 32, 33, 34], Ag-TiO2 [35], UC-P25 [38], WO3 [46], CdS [49], ZnFe2O4 [53], MnFe2O4 [54], NiFe2O4 [55], Bi2WO6 [58, 59], Bi2MoO6 [60], InNbO4 [61], and ZnSe [63], have been prepared by the hydrothermal process, while others such as TiO2 [11, 22, 26, 27], CuO [44], CdS [48], and CoFe2O4 [56] are prepared by the solvothermal process.

Li et al. have prepared P25-G nanocomposite using GO and P25 as raw materials via hydrothermal technique [8]. As illustrated in Figure 5, the photocatalysis determines that composite showed improved activity toward the photodegradation of methylene blue (MB).

Figure 5.

Photodegradation of MB under (a) UV light (λ = 365 nm) and (b) visible light (λ > 400 nm) over (1) P25, (2) P25-CNTs, and (3) P25-GR photocatalysts, respectively. (c) Schematic structure of P25-GR and process of the photodegradation of MB over P25-GR. (d) Bar plot showing the remaining MB in solution: (1) initial and equilibrated with (2) P25, (3) P25-CNTs, and (4) P25-GR in the dark after 10-min stirring. Pictures of the corresponding dye solutions are on the top for each sample. Reprinted with permission of the publisher [8].

Lee et al. synthesized graphene oxide (GO)-wrapped TiO2 nanoparticles by combining positively charged TiO2 nanoparticles with negatively charged GO nanosheets, as shown in SEM images in Figure 6. Furthermore, it demonstrates the reduction of graphene oxide to reduced graphene oxide and the crystallization of amorphous titania nanoparticles which occurred after a hydrothermal treatment.

Figure 6.

(A) Schematic illustration of synthesis steps for graphene-wrapped anatase TiO2 nanoparticles (NPs) and corresponding SEM images of (B) bare amorphous TiO2 NPs, (C) GO-wrapped amorphous TiO2 NPs, and (D) graphene-wrapped anatase TiO2 NPs (scale bar: 200 nm); (E) the suggested mechanism for the photocatalytic degradation of MB by graphene-wrapped anatase TiO2 NPs under visible light irradiation. Reprinted with permission of the publisher [8].

2.4 Microwave-assisted method

In situ microwave irradiation is a facile method which has been used for the simultaneous formation of metal oxide (e.g., TiO2 [17], ZnO [17, 41], CdS [47], ZnS [50]) and reduction of GO. The drawback of this process is that it did not show its fine control over the uniform size and surface distribution of nanoparticles on G surfaces.

2.5 Other methods

In addition to the abovementioned examples, graphene-based photocatalysts are synthesized by developing new synthetic strategies, e.g., electrospinning [10] and chemical vapor deposition (CVD) [64].

Zhao et al. pillared reduced graphene oxide platelets with carbon nanotubes using the CVD method with acetonitrile as the carbon source and nickel nanoparticles as the catalysts as shown in Figure 7.

Figure 7.

(A) Photocatalytic degradation for RhB under different experimental conditions with catalysts GOCNT-15-4 and P25. (B) Photocatalytic properties of different samples in degrading RhB. (C) Experimental steps of pillaring GO and RGO platelets with CNTs while energy diagram showing the proposed mechanism of photosensitized degradation of RhB under visible light irradiation. Reprinted with permission of the publisher [64].

Photocatalytic TiO2 films were prepared by Yoo et al. using RF magnetron sputtering and GO solutions with different concentrations of GO in ethanol which were coated on TiO2 films [67]. Graphene film was formed on the surface of TiO2 nanotube arrays through in situ electrochemical reduction of GO dispersion by cyclic voltammetry [19].

Advertisement

3. Photocatalysis

Due to widespread environmental applications, photocatalysis has fascinated an increasing consideration. The graphene-/graphene oxide-based photocatalyst revealed a significant improvement of photocatalytic degradation of methylene blue (MB) [1, 8, 11, 12, 15, 18, 21, 22, 26, 28, 30, 31, 32, 33, 35, 36, 40, 41, 43, 45, 48, 50, 52, 53, 54, 55, 56, 60, 61, 67, 68, 69], rhodamine B (RhB) [13, 20, 24, 27, 32, 42, 44, 51, 52, 56, 57, 58, 59, 62, 64, 73], methyl orange (MO) [9, 10, 14, 37, 38, 49, 63, 66, 71, 72, 74], anthracene-9-carboxylic acid (9-AnCOOH) [19], phenol [22, 54], 2,4-dichlorophenoxyacetic acid (2,4-D) [23], 2,4-dichlorophenol [61, 73], malachite green (MG) [29], 2-propanol [34], rhodamine 6G (Rh 6G) [39], rhodamine B 6G (RhB 6G) [46], orange ll [52], 2,4-dichlorophenol (2,4-DCP) [61], acid orange 7(AO 7) [64], and resazurin (RZ) [65], as well as photocatalytic reduction of Cr(VI) [17, 47, 71], along with photocatalytic antibacterial activity for killing E. coli bacteria [25] by UV [1, 8, 9, 10, 13, 14, 16, 17, 18, 19, 20, 21, 22, 23, 24, 26, 28, 29, 30, 31, 32, 33, 34, 37, 39, 40, 41, 42, 43, 44, 45, 50, 54, 65, 66, 67, 68, 69, 70, 71], as well as visible irradiation [1, 8, 9, 10, 11, 12, 13, 15, 16, 20, 22, 25, 27, 30, 31, 32, 33, 35, 36, 37, 38, 42, 45, 46, 47, 48, 49, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 67, 68, 72, 73, 74], in water which are briefly summarized in Table 1.

Photocatalysts Mass fraction Preparation strategy Photocatalytic experiments Performances as compared to reference photocatalyst Type of irradiation References
(1) rGO-based
P25-rGO 0.2% G Hydrothermal method Photodegradation of MB 1.17 times higher than P25; DP of 60% UV 1
5% 1.50 times
30% 0.97 times
0.2% 1.42 times higher than P25; DP of 28% Visible
5% 2.32 times
30% 0.75 times
P25-rGO 1.0% G Hydrothermal method Photodegradation of MB 3.40 or 1.21 times higher than P25 or P25-CNTs; DP of 25% or 70%, respectively (2% = 90 min) UV 2
4.33 or 1.18 times higher than P25 or P25-CNTs; DP of 15% or 55%, respectively (2% = 90 min) Visible
TiO2-rGO 10 mg G In situ growth strategy (thermal treatment) Degradation of MO 2.05 times higher than P25; DP of 40% UV 3
5.46 times higher than P25; 15% Visible
TiO2-rGO 0.75% G Electrospin-ning method Degradation of MO 1.51 times higher than TiO2; DP of 54% UV 4
2.04 times higher than TiO2; DP of approx. 22% Visible
TiO2-rGO 10 mg G Solvothermal method Photodegradation of MB 2.32 or 1.50 times higher than pure TiO2 or P25; DP of 25% or 39%, respectively Visible 5
30 mg 3.0 or 1.92 times
50 mg 2.88 or 1.84 times
TiO2-rGO 10 mg G In situ growth strategy (thermal reduction method) Photodegradation of MB 7.0 times higher than pure P25; DP of 10% Visible 6
TiO2-rGO No data In situ growth strategy (redox method) Photodegradation of RhB 1.16 times higher than P25 reaction rate constant = 0.0049 min−1 Visible 7
0.53 times higher than P25 reaction rate constant = 0.043 min−1 UV
SnO2-rGO 2.24 times higher than P25 reaction rate constant = 0.0049 min−1 Visible
0.62 times higher than P25 reaction rate constant = 0.043 min−1 UV
TiO2-rGO 20 mg G In situ growth strategy (simple liquid-phase deposition method) Photodegradation of MO 1.89 times higher than P25 and graphene; DP of 45% UV 8
TiO2-rGO No data Hydrothermal method Photodegradation of MB 13.04 or 10.62 times higher than P25 or anatase TiO2; reaction rate constant = 0.0026 min−1or 0.0032 min-1, respectively Visible 9
TiO2-rGO 20: 1 Hydrothermal method Photodegradation of RhB 1.63 times higher than P25; DP of 52% UV 10
3.33 times higher than P25; DP of 15% Visible
TiO2-rGO 0.8% G Microwave-assisted method Photocatalytic reduction of Cr(VI) 1.09 or 1.30 times higher than pure TiO2 or commercial P25 = removal rate of 83% or 70%, respectively UV 11
rGO-w-TiO2 1:10 Solution mixing method Photodegradation of MB 1.25 times higher than P25; DP of 80% UV 12
TiO2-rGO film No data Cyclic voltammetric reduction method Photodegradation of anthracene-9-carboxylic acid (9-AnCOOH) 2.13 times higher than bare TiO2 nanotubes; DP of 46% UV 13
TiO2-rGO 6.5% G In situ growth strategy (self-assembly synthesis) Photodegradation of RhB 3.92 times higher than TiO2; DP of 25% UV-vis 14
TiO2-rGO 0.6% G In situ growth strategy (self-assembly method) Photodegradation of MB 1.57 times higher than TiO2; reaction rate constant = 0.045 min−1 UV 15
TiO2-rGO No data Solvothermal method Photodegradation of phenol 1.68 times higher than P25; DP of 48% UV 16
3.10 times higher than P25; DP of 20% Visible
Photodegradation of MB 3.5 times higher than P25; DP of 20% Visible
TiO2-rGO film No data Solution mixing method Photodegradation of 2,4-dichlor-ophen-oxyacetic acid (2,4-D) 4.0 times higher than TiO2 film; reaction rate constant = 0.002 min−1 UV 17
TiO2-rGO 10% GO Hydrothermal method Photodegradation of RhB 4.0 or 2.94 times higher than pure TiO2 or P25; reaction rate constant = 0.05 or 0.068 min−1 UV 18
TiO2-rGO No data Solution mixing method Photocatalytic antibacterial activity for killing E. coli bacteria 7.55 times higher than TiO2; reaction rate constant = 0.0086 min−1 Visible 19
TiO2-rGO 0.3 mg GO Solvothermal method Photodegradation of MB 2.08 times higher than P25; DP of 40.8% UV 20
TiO2-rGO No data Solvothermal method Photodegradation of RhB 2.79 times higher than P25; reaction rate constant = 0.0162 min−1 Visible 21
TiO2-rGO 75% G Sonochemical method Photodegradation of MB 2.57 times higher than P25; reaction rate constant = 0.0054 min−1 UV 22
TiO2-rGO 10% G Hydrothermal method Photodegradation of Malachite green 3.09 times higher than TiO2 nanotubes; reaction rate constant = 0.0218 min−1 UV 23
TiO2-rGO No data Hydrothermal method Photodegradation of MB 1.46 times higher than P25; DP of 65% UV 24
2.41 times higher than P25; DP of 29% Visible
rGO @TiO2 1:3 Solution mixing method Photodegradation of MB 4.0 or 1.73 times higher than P25 or physical mixture of G-P25 (1:3); DP of 13% or 30%, respectively Visible 25
Photodegradation of MB 2.93–2.20 times higher than P25 or physical mixture of G-P25 (1:3); DP of 30–40% UV
TiO2-B-doped rGO 2 mg G Hydrothermal method Photodegradation of MB 4.30 times higher than TiO2; reaction rate constant = 0.010 min−1 UV-vis 26
Photodegradation of RhB 1.6 times higher than TiO2; reaction rate constant = 0.005 min−1
TiO2-N-doped rGO Photodegradation of MB 2.4 times higher than TiO2; reaction rate constant = 0.010 min−1
Photodegradation of RhB 3.2 times higher than TiO2; reaction rate constant = 0.005 min−1
TiO2-rGO-TiO2 0.01 g G Hydrothermal method Photodegradation of MB 4 times higher than TiO2 UV-vis 27
TiO2-rGO/MCM-41 0.05% G Hydrothermal method and Thermal method Photodegradation of 2-propanol 1.4 times higher than TiO2/MCM-41; conversion rate of 26% UV 28
0.15% 1.7 times
0.4% 1.27 times
0.6% 0.96 times
Ag-TiO2-rGO No data Hydrothermal and solution mixing method Photodegradation of MB Enhancement Visible 29
RutileTiO2-GQD/anatase TiO2-GQD 0.05 g G Solution mixing method Degradation of MB Enhancement for rutile TiO2/GQD than anatase TiO2/GQD Visible 30
Layered titanate rGO No data In situ growth strategy (self-assembly method) Photodegradation of MO Enhancement as compared to bulk-layered titanates or nanocrystalline-layered titanate UV-vis 31
UC-P25-rGO
UC = YF3:Yb3+,Tm3+
4 mg GO Hydrothermal method Photodegradation of MO 2.88 or times higher than P25 or P25-G or UC-P25; DP of 27% or 53% or 46%, respectively Visible 32
ZnO-rGO 0.6% G Microwave-assisted method Photocatalytic reduction of Cr(VI) 1.12 or 0.92 times higher than pure ZnO or P25; removal rate of 58 or 70%, respectively UV 33
0.8% G 1.46 or 1.21 times
1.0% G 1.68 or 1.40 times
ZnO-FGS 0.1 g GO In situ growth strategy (thermal method) Photodegradation of Rh 6G Enhancement UV 34
ZnO-rGO 0.1% G Solution mixing method (sonochemical) Photodegradation of MB 2.13 times higher than ZnO; reaction rate constant = 0.022 min−1 UV 35
0.5% 2.54 times
1.0% 3.13 times
2.0% 4.45 times
3.0% 4.13 times
5.0% 3.27 times
ZnO-rGO 1.1% G Microwave-assisted method Photodegradation of MB 1.29 times higher than ZnO; DP of 68% UV 36
ZnO@ rGO In situ growth strategy (chemical deposition method) Photodegradation of RhB 1.05 times higher than ZnO; DP of 95% UV 37
1.02 times higher than ZnO; DP of 98% Visible
ZnO-rGO 3.56% G Solution mixing method (ultrasonic method) Photodegradation of MB 2.25 times higher than ZnO; DP of 40% UV 38
CuO-rGO No data Solvothermal method Photodegradation of RhB in the presence of H2O2 2.50 times higher than ZnO; DP of 40% UV 39
SnO2-rGO 5% G In situ growth strategy (redox method) Photodegradation of MB 0.40 or times higher than SnO2; DP of 100% UV 40
24.86 times higher than SnO2; DP of 4% Visible
WO3-rGO 3.5% G Hydrothermal method Photodegradation of RhB 6G 2.2 or 53 times higher than WO3 nanorods or WO3 particles; reaction rate constant = 0.00167or 0.000069 min−1, respectively Visible 41
CdS-rGO 1.5% G Microwave-assisted method Photocatalytic reduction of Cr(VI) 1.16 times higher than CdS = removal rate of 79% Visible 42
CdS-rGO 5% G Solvothermal method Photodegradation of MB 2.5 times higher than CdS; DP of 37.6% Visible 43
CdS-rGO 0.01:1 Hydrothermal method Photodegradation of MO 7.86 times higher than CdS; reaction rate constant = 0.0075 min−1 Visible 44
ZnS-rGO No data Microwave-assisted method Photodegradation of MB 4 times higher than P25; DP of 25% UV 45
Cu-rGO No data In situ growth strategy (immersion method) Photodegradation of RhB 2.94 or 30.61 times higher than P25 or graphene; reaction rate constant = 0.0051 min−1 or 0.00049 min−1, respectively Visible 46
Au-rGO No data In situ growth strategy (chemical reduction) Photodegradation of RhB 1.77 times higher than P25; reaction rate constant = 0.0049 min−1 Visible 47
Photodegradation of MB 8.36 times
Photodegradation of orange II 0.19 times
ZnFe2O4-rGO 20% G Hydrothermal method Photodegradation of MB in the presence of H2O2 4.50 times higher than ZnFe2O4 (DP of 22% = 90 min) Visible 48
MnFe2O4-rGO 30% G Hydrothermal method Photodegradation of MB 9.62 times higher than MnFe2O 4 ; DP of 10% Visible 49
Photodegradation of MB 1.33 times higher than MnFe2O 4 ; DP of 75% UV
Photodegradation of phenol 1.13 times higher than MnFe2O 4 ; DP of 75% UV
NiFe2O4-rGO 25% G Hydrothermal method Photodegradation of MB Enhancement as compared to NiFe2O 4 ; reaction rate constant almost zero (no photocatalytic activity) Visible 50
CoFe2O4-rGO No data Solvothermal method Photodegradation of RhB and MB Enhancement Visible 51
Bi2WO6-rGO 1% G In situ growth strategy (refluxing method) Photodegradation of RhB 1.30 times higher than Bi2WO6; DP of 50% Visible 52
2.5% 1.40 times
5% 1.80 times
10% 1.10 times
15% 0.80 times
Bi2WO6-rGO 1% G Hydrothermal method Photodegradation of RhB Enhancement as compared to Bi2WO6 Visible 53
Bi2WO6-rGO No data Hydrothermal method Photodegradation of RhB 2.04 times higher than Bi2WO6; DP of 44% in 4 min Visible 54
Bi2MoO6-rGO 0.5% G Hydrothermal method Photodegradation of MB 2.45 times higher than pure Bi2MoO6; reaction rate constant 0.0037 min−1 Visible 55
1% 3.67 times
InNbO4-rGO No data Hydrothermal method Photodegradation of MB 1.87 times higher than InNbO4; reaction rate constant = 0.0185 min−1 Visible 56
Photodegra-dation of 2,4-dichloro-phenol 2.10 times higher than InNbO4 reaction rate constant = 0.0256 min−1
Ag@AgCl-rGO 0.22% G Solution mixing method Photodegradation of RhB 3.88 times higher than Ag@AgCl reaction rate constant = 0.060 min−1 Visible 57
0.44% 4.55 times
1.56% 5.1 times
ZnSe-N-doped rGO 18 mg G Hydrothermal method Photodegradation of MO Enhancement as compared to ZnSe; (no photocatalytic activity) Visible 58
CNT-rGO No data Chemical vapor deposition (CVD) method Photodegradation of RhB 4.28 times higher than P25; reaction rate constant = 0.0049 min−1 Visible 59
(2) GO-based
GO 1 mg GO Solution mixing method (modified Hummers’ method) Photocatalytic reduction of resazurin (RZ) No data UV 60
TiO2-GO No data In situ growth strategy Photodegradation of MO 2.27 times higher than pure P25; DP of 38.4% UV 61
TiO2-GO 0.03 mg GO RF magnetron sputtering followed by coating Photodegradation of MB 2.5 times higher than TiO2; DP of 20% UV 62
1.75 times Visible
TiO2-GO 1.2% GO Solution mixing method (simple colloidal blending method) Photodegradation of MB 4.51 times higher than P25 reaction rate constant = 0.0084 min−1 UV 63
4.3% 4.98 times
8.2% 8.59 times
1.2% 1.36 times higher than P25 reaction rate constant = 0.0033 min−1 Visible
4.3% 3.03 times
8.2% 7.15 times
TiO2-GO 50 mg GO In situ growth strategy Photodegradation of MB 1.41 times higher than P25; DP of 70% UV 64
TiO2-GO 500 mg GO In situ growth strategy (two phase assembling method) Photodegradation of acid orange 7 (AO 7) 11.59 times higher than P25 reaction rate constant = 0.0182 min−1 UV 65
TiO2-GO No data In situ growth strategy (thermal treatment method) Photodegradation of MO 7.44 times higher than P25; reaction rate constant = 0.0426 min−1 UV 66
Photocatalytic reduction of Cr(VI) 5.44 times higher than P25; conversion rate = 0.0127 min−1
TiO2-GO 0.13% C element In situ growth strategy (self-assembly method) Photodegradation of MO 1.18 times higher than pure P25; DP of 22% Visible 67
0.14% 1.59 times
0.25% 1.0 times
0.51% 0.82 times
g-C3N4-GO 1 g GO Solution mixing method (sonochemical method) Photodegradation of RhB and 2,4-dichloro-phenol 1.90 times higher than g-C3N4; DP of 49.5% Visible 68
Ag/AgCl/GO No data Solution mixing method (surfactant-assisted assembly protocol via an oil/water microemulsion) Photodegradation of MO 2.84 times higher than Ag/AgCl; DP of 25% Visible 69
Ag/AgBr/GO Photodegradation of MO 3.40 times higher than Ag/AgBr; DP of 25% Visible

Table 1.

Photocatalytic degradation of pollutants.

References

  1. 1. Zhang Y, Tang ZR, Fu X, Xu YJ. TiO2-graphene nanocomposites for gas-phase photocatalytic degradation of volatile aromatic pollutant: Is TiO2-graphene truly different from other TiO2-carbon composite materials? ACS Nano. 2010;4:7303-7314
  2. 2. Huang X, Qi X, Boey F, Zhang H. Graphene-based composites. Chemical Society Reviews. 2012;41:666-686
  3. 3. Han L, Wang P, Dong S. Progress in graphene-based photoactive nanocomposites as a promising class of photocatalyst. Nanoscale. 2012;4:5814-5825
  4. 4. Xiang Q , Yu J, Jaroniec M. Graphene-based semiconductor photocatalysts. Chemical Society Reviews. 2012;41:782-796
  5. 5. Zhang N, Zhang Y, Xu YJ. Recent progress on graphene-based photocatalysts: Current status and future perspectives. Nanoscale. 2012;4:5792-5813
  6. 6. Le NH, Seema H, Kemp KC, Ahmed N, Tiwari JN, Park S, et al. Solution-processable conductive micro-hydrogels of nanoparticle/graphene platelets produced by reversible self-assembly and aqueous exfoliation. Journal of Materials Chemistry A. 2013;1:12900-12908
  7. 7. Kemp KC, Seema H, Saleh M, Le NH, Mahesh K, Chandra V, et al. Environmental applications using graphene composites: Water remediation and gas adsorption. Nanoscale. 2013;5:3149-3171
  8. 8. Zhang H, Lv X, Li Y, Wang Y, Li J. P25-graphene composite as a high performance photocatalyst. ACS Nano. 2009;4:380-386
  9. 9. Wang F, Zhang K. Physicochemical and photocatalytic activities of self-assembling TiO2 nanoparticles on nanocarbons surface. Current Applied Physics. 2012;12:346-352
  10. 10. Zhu P, Nair AS, Shengjie P, Shengyuan Y, Ramakrishna S. Facile fabrication of TiO2-graphene composite with enhanced photovoltaic and photocatalytic properties by electrospinning. ACS Applied Materials & Interfaces. 2012;4:581-585
  11. 11. Zhou K, Zhu Y, Yang X, Jiang X, Li C. Preparation of graphene-TiO2 composites with enhanced photocatalytic activity. New Journal of Chemistry. 2011;35:353-359
  12. 12. Zhang Y, Pan C. TiO2/graphene composite from thermal reaction of graphene oxide and its photocatalytic activity in visible light. Journal of Materials Science. 2011;46:2622-2626
  13. 13. Zhang J, Xiong Z, Zhao XS. Graphene-metal-oxide composites for the degradation of dyes under visible light irradiation. Journal of Materials Chemistry. 2011;21:3634-3640
  14. 14. Zhang H, Xu P, Du G, Chen Z, Oh K, Pan D, et al. A facile one-step synthesis of TiO2/graphene composites for photodegradation of methyl orange. Nano Research. 2011;4:274-283
  15. 15. Lee JS, You KH, Park CB. Highly photoactive, low bandgap TiO2 nanoparticles wrapped by graphene. Advanced Materials. 2012;24:1084-1088
  16. 16. Wang F, Zhang K. Reduced graphene oxide-TiO2 nanocomposite with high photocatalystic activity for the degradation of rhodamine B. Journal of Molecular Catalysis A: Chemical. 2011;345:101-107
  17. 17. Liu X, Pan L, Lv T, Zhu G, Lu T, Sun Z, et al. Microwave-assisted synthesis of TiO2-reduced graphene oxide composites for the photocatalytic reduction of Cr (VI). RSC Advances. 2011;1:1245-1249
  18. 18. Seema H, Shirinfar B, Shi G, Youn IS, Ahmed N. Facile synthesis of a selective biomolecule chemosensor and fabrication of its highly fluorescent graphene complex. The Journal of Physical Chemistry B. 2017;121:5007-5016
  19. 19. Liu C, Teng Y, Liu R, Luo S, Tang Y, Chen L, et al. Fabrication of graphene films on TiO2 nanotube arrays for photocatalytic application. Carbon. 2011;49:5312-5320
  20. 20. Li N, Liu G, Zhen C, Li F, Zhang L, Cheng HM. Battery performance and photocatalytic activity of mesoporous anatase TiO2 nanospheres/graphene composites by template-free self-assembly. Advanced Functional Materials. 2011;21:1717-1722
  21. 21. Du J, Lai X, Yang N, Zhai J, Kisailus D, Su F, et al. Hierarchically ordered macro- mesoporous TiO2-graphene composite films: Improved mass transfer, reduced charge recombination, and their enhanced photocatalytic activities. ACS Nano. 2010;5:590-596
  22. 22. Jiang B, Tian C, Zhou W, Wang J, Xie Y, Pan Q , et al. In situ growth of TiO2 in interlayers of expanded graphite for the fabrication of TiO2-graphene with enhanced photocatalytic activity. Chemistry–A European Journal. 2011;17:8379-8387
  23. 23. Shirinfar B, Seema H, Ahmed N. Charged probes: Turn-on selective fluorescence for RNA. Organic & Biomolecular Chemistry. 2018;16:164-168
  24. 24. Liang Y, Wang H, Casalongue HS, Chen Z, Dai H. TiO2 nanocrystals grown on graphene as advanced photocatalytic hybrid materials. Nano Research. 2010;3:701-705
  25. 25. Akhavan O, Ghaderi E. Photocatalytic reduction of graphene oxide nanosheets on TiO2 thin film for photoinactivation of bacteria in solar light irradiation. The Journal of Physical Chemistry C. 2009;113:20214-20220
  26. 26. Jiang B, Tian C, Pan Q , Jiang Z, Wang JQ , Yan W, et al. Enhanced photocatalytic activity and electron transfer mechanisms of graphene/TiO2 with exposed {001} facets. The Journal of Physical Chemistry C. 2011;115:23718-23725
  27. 27. Sun L, Zhao Z, Zhou Y, Liu L. Anatase TiO2 nanocrystals with exposed {001} facets on graphene sheets via molecular grafting for enhanced photocatalytic activity. Nanoscale. 2012;4:613-620
  28. 28. Guo J, Zhu S, Chen Z, Li Y, Yu Z, Liu Q , et al. Sonochemical synthesis of TiO2 nanoparticles on graphene for use as photocatalyst. Ultrasonics Sonochemistry. 2011;18:1082-1090
  29. 29. Perera SD, Mariano RG, Vu K, Nour N, Seitz O, Chabal Y, et al. Hydrothermal synthesis of graphene-TiO2 nanotube composites with enhanced photocatalytic activity. ACS Catalysis. 2012;2:949-956
  30. 30. Liu B, Huang Y, Wen Y, Du L, Zeng W, Shi Y, et al. Highly dispersive {001} facets-exposed nanocrystalline TiO2 on high quality graphene as a high performance photocatalyst. Journal of Materials Chemistry. 2012;22:7484-7491
  31. 31. Zhao D, Sheng G, Chen C, Wang X. Enhanced photocatalytic degradation of methylene blue under visible irradiation on graphene@ TiO2 dyade structure. Applied Catalysis B: Environmental. 2012;111:303-308
  32. 32. Gopalakrishnan K, Joshi HM, Kumar P, Panchakarla LS, Rao CN. Selectivity in the photocatalytic properties of the composites of TiO2nanoparticles with B-and N-doped graphenes. Chemical Physics Letters. 2011;511:304-308
  33. 33. Seema H, Kemp KC, Le NH, Park SW, Chandra V, Lee JW, et al. Highly selective CO2 capture by S-doped microporous carbon materials. Carbon. 2014;66:320-326
  34. 34. Kamegawa T, Yamahana D, Yamashita H. Graphene coating of TiO2 nanoparticles loaded on mesoporous silica for enhancement of photocatalytic activity. The Journal of Physical Chemistry C. 2010;114:15049-15053
  35. 35. Wen Y, Ding H, Shan Y. Preparation and visible light photocatalytic activity of Ag/TiO2/graphene nanocomposite. Nanoscale. 2011;3:4411-4417
  36. 36. Zhuo S, Shao M, Lee ST. Upconversion and downconversion fluorescent graphene quantum dots: Ultrasonic preparation and photocatalysis. ACS Nano. 2012;6:1059-1064
  37. 37. Kim IY, Lee JM, Kim TW, Kim HN, Kim HI, Choi W, et al. A strong electronic coupling between graphene nanosheets and layered titanate nanoplates: A soft-chemical route to highly porous nanocomposites with improved photocatalytic activity. Small. 2012;8:1038-1048
  38. 38. Ren L, Qi X, Liu Y, Huang Z, Wei X, Li J, et al. Upconversion-P25-graphene composite as an advanced sunlight driven photocatalytic hybrid material. Journal of Materials Chemistry. 2012;22:11765-11771
  39. 39. Yang Y, Ren L, Zhang C, Huang S, Liu T. Facile fabrication of functionalized graphene sheets (FGS)/ZnO nanocomposites with photocatalytic property. ACS Applied Materials & Interfaces. 2011;3:2779-2785
  40. 40. Xu T, Zhang L, Cheng H, Zhu Y. Significantly enhanced photocatalytic performance of ZnO via graphene hybridization and the mechanism study. Applied Catalysis B: Environmental. 2011;101:382-387
  41. 41. Lv T, Pan L, Liu X, Lu T, Zhu G, Sun Z. Enhanced photocatalytic degradation of methylene blue by ZnO-reduced graphene oxide composite synthesized via microwave-assisted reaction. Journal of Alloys and Compounds. 2011;509:10086-10091
  42. 42. Li B, Cao H. ZnO@ graphene composite with enhanced performance for the removal of dye from water. Journal of Materials Chemistry. 2011;21:3346-3349
  43. 43. Luo QP, Yu XY, Lei BX, Chen HY, Kuang DB, Su CY. Reduced graphene oxide-hierarchical ZnO hollow sphere composites with enhanced photocurrent and photocatalytic activity. The Journal of Physical Chemistry C. 2012;116:8111-8117
  44. 44. Liu S, Tian J, Wang L, Luo Y, Sun X. One-pot synthesis of CuO nanoflower-decorated reduced graphene oxide and its application to photocatalytic degradation of dyes. Catalysis Science & Technology. 2012;2:339-344
  45. 45. Seema H, Kemp KC, Chandra V, Kim KS. Graphene-SnO2 composites for highly efficient photocatalytic degradation of methylene blue under sunlight. Nanotechnology. 2012;23:355705
  46. 46. An X, Jimmy CY, Wang Y, Hu Y, Yu X, Zhang G. WO3 nanorods/graphene nanocomposites for high-efficiency visible-light-driven photocatalysis and NO2 gas sensing. Journal of Materials Chemistry. 2012;22:8525-8531
  47. 47. Liu X, Pan L, Lv T, Zhu G, Sun Z, Sun C. Microwave-assisted synthesis of CdS-reduced graphene oxide composites for photocatalytic reduction of Cr (vi). Chemical Communications. 2011;47:11984-11986
  48. 48. Wang X, Tian H, Yang Y, Wang H, Wang S, Zheng W, et al. Reduced graphene oxide/CdS for efficiently photocatalytic degradation of methylene blue. Journal of Alloys and Compounds. 2012;524:5-12
  49. 49. Ye A, Fan W, Zhang Q , Deng W, Wang Y. CdS–graphene and CdS–CNT nanocomposites as visible-light photocatalysts for hydrogen evolution and organic dye degradation. Catalysis Science & Technology. 2012;2:969-978
  50. 50. Hu H, Wang X, Liu F, Wang J, Xu C. Rapid microwave-assisted synthesis of graphene nanosheets–zinc sulfide nanocomposites: Optical and photocatalytic properties. Synthetic Metals. 2011;161:404-410
  51. 51. Xiong Z, Zhang LL, Zhao XS. Visible-light-induced dye degradation over copper-modified reduced graphene oxide. Chemistry–A European Journal. 2011;17:2428-2434
  52. 52. Xiong Z, Zhang LL, Ma J, Zhao XS. Photocatalytic degradation of dyes over graphene-gold nanocomposites under visible light irradiation. Chemical Communications. 2010;46:6099-6101
  53. 53. Fu Y, Wang X. Magnetically separable ZnFe2O4-graphene catalyst and its high photocatalytic performance under visible light irradiation. Industrial & Engineering Chemistry Research. 2011;50:7210-7218
  54. 54. Fu Y, Xiong P, Chen H, Sun X, Wang X. High photocatalytic activity of magnetically separable manganese ferrite-graphene heteroarchitectures. Industrial & Engineering Chemistry Research. 2012;51:725-731
  55. 55. Fu Y, Chen H, Sun X, Wang X. Graphene-supported nickel ferrite: A magnetically separable photocatalyst with high activity under visible light. AIChE Journal. 2012;58:3298-3305
  56. 56. Min YL, Zhang K, Chen YC, Zhang YG. Enhanced photocatalytic performance of Bi2WO6 by graphene supporter as charge transfer channel. Separation and Purification Technology. 2012;86:98-105
  57. 57. Zhou F, Shi R, Zhu Y. Significant enhancement of the visible photocatalytic degradation performances of γ-Bi2MoO6 nanoplate by graphene hybridization. Journal of Molecular Catalysis A: Chemical. 2011;340:77-82
  58. 58. Zhang X, Quan X, Chen S, Yu H. Constructing graphene/InNbO4 composite with excellent adsorptivity and charge separation performance for enhanced visible-light-driven photocatalytic ability. Applied Catalysis B: Environmental. 2011;105:237-422
  59. 59. Ying H, Wang ZY, Guo ZD, Shi ZJ, YANG SF. Reduced graphene oxide-modified Bi2WO6 as an improved photocatalyst under visible light. Acta Physico-Chimica Sinica. 2011;27:1482-1486
  60. 60. Bai S, Shen X, Zhong X, Liu Y, Zhu G, Xu X, et al. One-pot solvothermal preparation of magnetic reduced graphene oxide-ferrite hybrids for organic dye removal. Carbon. 2012;50:2337-2346
  61. 61. Gao E, Wang W, Shang M, Xu J. Synthesis and enhanced photocatalytic performance of graphene-Bi2WO6 composite. Physical Chemistry Chemical Physics. 2011;13:2887-2893
  62. 62. Zhang H, Fan X, Quan X, Chen S, Yu H. Graphene sheets grafted Ag@AgCl hybrid with enhanced plasmonic photocatalytic activity under visible light. Environmental Science & Technology. 2011;45:5731-5736
  63. 63. Chen P, Xiao TY, Li HH, Yang JJ, Wang Z, Yao HB, et al. Nitrogen-doped graphene/ZnSe nanocomposites: Hydrothermal synthesis and their enhanced electrochemical and photocatalytic activities. ACS Nano. 2011;6:712-719
  64. 64. Zhang LL, Xiong Z, Zhao XS. Pillaring chemically exfoliated graphene oxide with carbon nanotubes for photocatalytic degradation of dyes under visible light irradiation. ACS Nano. 2010;4:7030-7036
  65. 65. Krishnamoorthy K, Mohan R, Kim SJ. Graphene oxide as a photocatalytic material. Applied Physics Letters. 2011;98:244101
  66. 66. Zhang Q , He Y, Chen X, Hu D, Li L, Yin T, et al. Structure and photocatalytic properties of TiO2-graphene oxide intercalated composite. Chinese Science Bulletin. 2011;56:331-339
  67. 67. Yoo DH, Cuong TV, Pham VH, Chung JS, Khoa NT, Kim EJ, et al. Enhanced photocatalytic activity of graphene oxide decorated on TiO2 films under UV and visible irradiation. Current Applied Physics. 2011;11:805-808
  68. 68. Nguyen-Phan TD, Pham VH, Shin EW, Pham HD, Kim S, Chung JS, et al. The role of graphene oxide content on the adsorption-enhanced photocatalysis of titanium dioxide/graphene oxide composites. Chemical Engineering Journal. 2011;170:226-232
  69. 69. Liu J, Bai H, Wang Y, Liu Z, Zhang X, Sun DD. Self-assembling TiO2 nanorods on large graphene oxide sheets at a two-phase interface and their anti-recombination in photocatalytic applications. Advanced Functional Materials. 2010;20:4175-4181
  70. 70. Liu J, Liu L, Bai H, Wang Y, Sun DD. Gram-scale production of graphene oxide-TiO2 nanorod composites: Towards high-activity photocatalytic materials. Applied Catalysis B: Environmental. 2011;106:76-82
  71. 71. Jiang G, Lin Z, Chen C, Zhu L, Chang Q , Wang N, et al. TiO2 nanoparticles assembled on graphene oxide nanosheets with high photocatalytic activity for removal of pollutants. Carbon. 2011;49:2693-2701
  72. 72. Chen C, Cai W, Long M, Zhou B, Wu Y, Wu D, et al. Synthesis of visible-light responsive graphene oxide/TiO2 composites with p/n heterojunction. ACS Nano. 2010;4:6425-6432
  73. 73. Liao G, Chen S, Quan X, Yu H, Zhao H. Graphene oxide modified gC3N4 hybrid with enhanced photocatalytic capability under visible light irradiation. Journal of Materials Chemistry. 2012;22:2721-2726
  74. 74. Zhu M, Chen P, Liu M. Graphene oxide enwrapped Ag/AgX (X = Br, Cl) nanocomposite as a highly efficient visible-light plasmonic photocatalyst. ACS Nano. 2011;5:4529-4536

Written By

Humaira Seema

Reviewed: 12 February 2019 Published: 23 September 2019