异质结光催化材料的新进展

doi:10.1016/S1872-2067(20)63698-1

催化学报 ›› 2021, Vol. 42 ›› Issue (5): 710-730.DOI: 10.1016/S1872-2067(20)63698-1

异质结光催化材料的新进展

王宗鹏^a^,^b, 林志萍^a^,^c, 申士杰^a^,^c, 钟文武^a^,^c^,^*(), 曹少文^b^,^#()

^a台州学院高等研究院, 浙江台州318000
^b武汉理工大学, 材料复合新技术国家重点实验室, 湖北武汉430070
^c台州学院医药化工与材料工程学院, 浙江台州318000

收稿日期:2020-04-29 接受日期:2020-04-29 出版日期:2021-05-18 发布日期:2021-01-29
通讯作者: 钟文武,曹少文
基金资助:
科技部重点研发项目(2018YFE0202601);国家自然科学基金(11947070);国家自然科学基金(51572183);国家自然科学基金(51922081);国家自然科学基金(21773179);浙江省一流学科(P61021902);浙江省自然科学基金(LTY20E020001)

Advances in designing heterojunction photocatalytic materials

Zongpeng Wang^a^,^b, Zhiping Lin^a^,^c, Shijie Shen^a^,^c, Wenwu Zhong^a^,^c^,^*(), Shaowen Cao^b^,^#()

^aSchool of Advanced Study, Taizhou University, Taizhou 318000, Zhejiang, China
^bState Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, Hubei, China
^cSchool of Pharmaceutical and Material Engineering, Taizhou University, Taizhou 318000, Zhejiang, China

Received:2020-04-29 Accepted:2020-04-29 Online:2021-05-18 Published:2021-01-29
Contact: Wenwu Zhong,Shaowen Cao
About author:^# E-mail: swcao@whut.edu.cn
^* E-mail: zhongww@tzc.edu.cn;
Supported by:
Key Research and Development of Ministry of Science and Technology of China(2018YFE0202601);National Natural Science Foundation of China(11947070);National Natural Science Foundation of China(51572183);National Natural Science Foundation of China(51922081);National Natural Science Foundation of China(21773179);Materials Science & Engineering of Zhejiang Province First-Class Discipline(P61021902);Natural Science Foundation of Zhejiang Province(LTY20E020001)

摘要/Abstract

摘要：

伴随着人类文明的快速发展, 一些危机慢慢显露出来, 例如能源危机、环境污染和全球变暖. 2019年5月11日, Mauna Loa天文台报告, 大气中的二氧化碳水平超过415 ppm, 达到人类历史上的最高记录, 欧盟随后于2019年11月宣布了气候紧急状态. 因此, 绿色能源技术已成为迫切需求, 以减少化石燃料的使用, 并减少污染物的产生.

光催化是直接利用太阳能的技术, 可以应用于水分解产氢、CO₂还原、降解有机污染物、促进有机物合成等, 是解决能源和环境问题的最有前途的技术之一. 光催化剂是光催化技术的核心. 目前, 许多半导体材料可作为光催化剂, 并已被充分地研究, 例如TiO₂、CdS、ZnO、BiVO₄和C₃N₄等. 然而, 单一的半导体材料具有一些缺点, 阻碍了它们的实际应用. 其中, 限制这些半导体材料光催化活性的一个关键问题是, 光生电子-空穴对容易快速复合而不是参与光催化反应. 例如, ZnO中激子的寿命估计仅为数百皮秒, 大多数激子来不及参与到氧化还原反应中.

为了抑制电子-空穴对的复合, 需要应用特殊的策略. 构建异质结光催化材料已成为最有前途的方法之一. 通常, 可以根据相邻材料的能带结构, 将异质结分为以下几种类型: PN型异质结, II型异质结, Schottky型异质结和S型异质结. 以上异质结大都是由两种半导体材料复合而形成的. 除此之外, 还可以根据形成异质结的特殊材料, 补充两种特殊的异质结类型, 即晶面异质结和石墨烯基异质结. 晶面异质结是由同一材料, 由于暴露不同的晶面而形成的. 石墨烯具有独特的能带结构、极大的比表面积及优良的导电性, 可以与其他半导体形成各种类型的异质结. 这些异质结材料能有效抑制电子-空穴对的复合, 从而提高材料整体的光催化活性, 也已成为光催化剂家族的重要分支. 本文详细介绍了以上各种类型的异质结光催化剂的最新进展, 概述了实现高性能异质结光催化剂的基本策略, 并对异质结光催化剂未来发展方向进行了一些探讨.

关键词: 光催化剂, 异质结, 可再生能源, 电荷转移, 氧化还原能力

Abstract:

Under the background of increasing energy crisis and global warming, semiconductor-based photocatalysis has received tremendous attention due to its potential application in green energy production, CO₂ reduction and pollutant degradation. The photocatalytic activity of semiconductors, however, remains low due to issues like fast recombination of photo-generated electron-hole pairs, limited electron mobility, restricted optical absorption or insufficient active sites. Designing appropriate heterojunctions is proved to be a promising method to address most of these issues and thus to improve the photocatalytic performance. In this review, the working mechanism of various heterojunctions is presented systematically. The most recent advances of strategies in designing and preparing efficient heterojunction photocatalysts are further summarized and some perspectives on the future directions in this field are provided.

Key words: Photocatalyst, Heterojunction, Renewable energy, Charge transfer, Redox ability

王宗鹏, 林志萍, 申士杰, 钟文武, 曹少文. 异质结光催化材料的新进展[J]. 催化学报, 2021, 42(5): 710-730.

Zongpeng Wang, Zhiping Lin, Shijie Shen, Wenwu Zhong, Shaowen Cao. Advances in designing heterojunction photocatalytic materials[J]. Chinese Journal of Catalysis, 2021, 42(5): 710-730.

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Heterojunctions	Similarity	Difference
Type II and S-scheme heterojunctions	Similar band alignment	Recombination pathway
Type II and PN heterojunctions	Similar charge separation pathway	The built-in field is against the charge separation for Type II heterojunction
PN and Schottky heterojunctions	Strong internal field	Schottky barrier is formed for Schottky heterojunction

Heterojunctions	Similarity	Difference
Type II and S-scheme heterojunctions	Similar band alignment	Recombination pathway
Type II and PN heterojunctions	Similar charge separation pathway	The built-in field is against the charge separation for Type II heterojunction
PN and Schottky heterojunctions	Strong internal field	Schottky barrier is formed for Schottky heterojunction

Heterojunction	Application	Performance	Year	Ref.
WO₃/TiO₂	Stearic acid degradation	14 times higher than pure TiO₂	2017	[60]
NiO/TiO₂	H₂ generation	22 times greater than TiO₂	2018	[61]
CsPbBrCl₂/g-C₃N₄	Organic effluents degradation	Degrading 94% of Eosin B dye within 120 min	2019	[62]
CdS/ZnSe	Water splitting	Higher carrier mobility	2018	[63]
SnO_x/Zn₂SnO₄	Degradation of methyl orange	Complete decolorization in 30 min	2017	[64]
CuSbSe₂/TiO₂	Degradation of organic dyes	21.08% increase in the degradation efficiency than TiO₂	2019	[65]
WO₃/BiOBr	Oxidation of amine to imine	2 times higher than WO₃	2020	[66]
ZnO/Ag₂S	Anti-bacteria	Significant antibacterial activity	2020	[67]
g-C₃N₄/ZnTe	Photosynthesis of ethanol	Generation rate of 17.1 μmol cm^-2 h^-1 (at -1.1 V vs. Ag/AgCl)	2019	[68]
I-BiOCl/I-BiOBr	Degradation of methyl orange	7 times than BiOBr	2017	[69]
La₂Ti₂O₇/In₂S₃	H₂ generation	18 times higher than physical mixtures of La₂Ti₂O₇ and In₂S₃	2019	[70]
BiVO₄/WO₃	Photoanode	2.15 times enhancement than WO₃	2016	[71]
Pt/TiO₂/CdS/Co₃O₄	H₂ generation	A generation rate of 2000 μmol g^-1 h^-1	2018	[72]
VO₂/CuWO₄	Degradation of azure II	Degrading 83.8% in 80 min	2018	[73]
ZnS/g-C₃N₄	MB degradation	2.6 times better compared to bare g-C₃N₄	2017	[74]
Cu₂O/g-C₃N₄	H₂ generation	4 times higher than pure g-C₃N₄	2017	[75]
CuS/BiFeO₃	Degradation of alachlor	95% degradation within 1 h	2018	[76]
Cu₂O/SnO₂	RhB degradation	2-fold higher than individual SnO₂	2016	[77]
S/CdS	H₂ generation	8.14 mmol h^-1	2017	[78]
Mn₃O₄/MnO₂	MB degradation	93.5% degradation within 1 h	2017	[79]
SnS₂/H‐TiO₂/Ti	H₂ generation	70 times higher than SnS₂/TiO₂/Ti	2019	[80]
TiO₂/CdIn₂S₄	H₂ generation	5.5 times higher than bare TiO₂	2018	[81]
IO/CdS	Degradation of xylenol blue	97.6% degradation within 3 h	2019	[82]
g-C₃N₄/P25	H₂ generation	24.5 times higher than pure g-C₃N₄	2019	[83]
ZnIn₂S₄/BiPO₄	TC degradation	84% degradation within 80 min	2019	[84]
Bi₂SiO₅/BiPO₄	Phenol degradation	4.36 timed higher than Bi₂SiO₅	2018	[85]
g-C₃N₄/Nb₂O₅	RhB degradation	9.4 times higher than Nb₂O₅	2017	[86]

Heterojunction	Application	Performance	Year	Ref.
WO₃/TiO₂	Stearic acid degradation	14 times higher than pure TiO₂	2017	[60]
NiO/TiO₂	H₂ generation	22 times greater than TiO₂	2018	[61]
CsPbBrCl₂/g-C₃N₄	Organic effluents degradation	Degrading 94% of Eosin B dye within 120 min	2019	[62]
CdS/ZnSe	Water splitting	Higher carrier mobility	2018	[63]
SnO_x/Zn₂SnO₄	Degradation of methyl orange	Complete decolorization in 30 min	2017	[64]
CuSbSe₂/TiO₂	Degradation of organic dyes	21.08% increase in the degradation efficiency than TiO₂	2019	[65]
WO₃/BiOBr	Oxidation of amine to imine	2 times higher than WO₃	2020	[66]
ZnO/Ag₂S	Anti-bacteria	Significant antibacterial activity	2020	[67]
g-C₃N₄/ZnTe	Photosynthesis of ethanol	Generation rate of 17.1 μmol cm^-2 h^-1 (at -1.1 V vs. Ag/AgCl)	2019	[68]
I-BiOCl/I-BiOBr	Degradation of methyl orange	7 times than BiOBr	2017	[69]
La₂Ti₂O₇/In₂S₃	H₂ generation	18 times higher than physical mixtures of La₂Ti₂O₇ and In₂S₃	2019	[70]
BiVO₄/WO₃	Photoanode	2.15 times enhancement than WO₃	2016	[71]
Pt/TiO₂/CdS/Co₃O₄	H₂ generation	A generation rate of 2000 μmol g^-1 h^-1	2018	[72]
VO₂/CuWO₄	Degradation of azure II	Degrading 83.8% in 80 min	2018	[73]
ZnS/g-C₃N₄	MB degradation	2.6 times better compared to bare g-C₃N₄	2017	[74]
Cu₂O/g-C₃N₄	H₂ generation	4 times higher than pure g-C₃N₄	2017	[75]
CuS/BiFeO₃	Degradation of alachlor	95% degradation within 1 h	2018	[76]
Cu₂O/SnO₂	RhB degradation	2-fold higher than individual SnO₂	2016	[77]
S/CdS	H₂ generation	8.14 mmol h^-1	2017	[78]
Mn₃O₄/MnO₂	MB degradation	93.5% degradation within 1 h	2017	[79]
SnS₂/H‐TiO₂/Ti	H₂ generation	70 times higher than SnS₂/TiO₂/Ti	2019	[80]
TiO₂/CdIn₂S₄	H₂ generation	5.5 times higher than bare TiO₂	2018	[81]
IO/CdS	Degradation of xylenol blue	97.6% degradation within 3 h	2019	[82]
g-C₃N₄/P25	H₂ generation	24.5 times higher than pure g-C₃N₄	2019	[83]
ZnIn₂S₄/BiPO₄	TC degradation	84% degradation within 80 min	2019	[84]
Bi₂SiO₅/BiPO₄	Phenol degradation	4.36 timed higher than Bi₂SiO₅	2018	[85]
g-C₃N₄/Nb₂O₅	RhB degradation	9.4 times higher than Nb₂O₅	2017	[86]

Heterojunction	Application	Performance	Year	Ref.
Fe₂O₃/BiOI	RhB degradation	4.24 times higher than single BiOI	2016	[93]
Cu₃P/g-C₃N₄	Hydrogen generation	95 times higher activity than bare g-C₃N₄	2018	[94]
MoSe₂/Bi₂WO₆	Degradation of gas-phase toluene	7 times higher compared with pure MoSe₂	2018	[95]
ZnO/MnWO₄	Degradations of RhB, MB, MO	22.5, 17.7, 26.8 times higher than that of the ZnO sample in degradations of RhB, MB, MO	2018	[96]
BiOI/BiPO₄	Degradation of tetracycline	1.98 times and 2.46 times higher than BiOI and BiPO₄	2019	[97]
Ag₂S/BiVO₄	Degradation of tetracycline	90.2% degradation efficiency	2019	[99]
Ag₂O/AgNbO₃	Degradation of RhB	Degradation efficiency of 95.4% within 90 min	2019	[100]
MoS₂/MgIn₂S₄	NH₃ production	4 and 7 times higher than bare MoS2 and MgIn₂S₄	2020	[101]
Bi₂O₃/MoS₂	Hydrogen generation	10 times higher than pure Bi₂O₃ and MoS₂	2020	[102]
ZnFe₂O₄/SnS₂	Degradation of MO	1.7 times higher than individual ZnFe₂O₄	2020	[103]
BiVO₄@MoS₂	Reduction of Cr⁶⁺	76.5 % Cr⁶⁺ reduced within 90 min	2016	[104]
g-C₃N₄/Bi₄Ti₃O₁₂	Degradation of acid orange-II	2.85 times higher than pure Bi₄Ti₃O₁₂	2016	[105]
WO₆/BiOI	Antifouling	99.99% P. aeruginosa, E. coli and S. aureus killed within 60 min	2016	[106]
BiPO₄/BiOCl	MO degradation	A degradation efficiency of 98% within 14 min	2015	[107]
Ag₂O/Bi₅O₇I	Degradation of Bisphenol A and phenol	A degradation efficiency of 99.9% within 40 min	2017	[108]
BiOI/CeO₂	MO degradation	A degradation efficiency of 93.75% within 50 min	2017	[109]
Ag₂O/TiO₂	PNP degradation	7.7 times higher than TiO₂	2015	[110]
CdWO₄/BiOBr	Degradation of RhB	2.8 times better than BiOBr	2016	[111]
BiPO₄/BiOBr	o-Dichlorobenzene removal	A removal efficiency of 53.6%	2017	[112]
CuO/ZnO	Degradation of RhB and CR	Complete degradation within 60 min	2017	[113]
Ag₂O/BiOCOOH	Degradation of RhB	96.8% degradation within 60 min	2017	[114]
Bi₂Sn₂O₇/Ag₂CrO₄	Degradation of RhB, MO and MB	97.5%, 90.4% and 99.8% degradation within 120 min, respectively	2018	[115]
Co₃O₄/Bi₂O₂CO₃	Degradation of MO	90% degradation within 150 min	2017	[116]
BiOI/TiO₂	Selective hydroxylation of phenol	A selectivity of 92.1%	2018	[117]

异质结光催化材料的新进展

Advances in designing heterojunction photocatalytic materials

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Metrics

Heterojunction	Application	Performance	Year	Ref.
Ru/TiO₂	Water splitting	H₂ evolution rate of 40.2 µmol h^-1 g^-1	2016	[125]
Au/Cu₂O	MO degradation	1.2 times higher than pure Cu2O microcubes	2016	[127]
TiO₂/NC-Ru	Oxidation of benzyl alcohol	99% selectivity	2019	[128]
TaON/Ni	Reduction of CO₂ to CH₄	5.1 times higher than pristine TaON	2019	[129]
Bi₂MoO₆/Ti₃C₂	Molecular oxygen activation	5.6 times higher than pristine samples	2020	[130]
CoSe₂/CdS_0.95Se_0.05	H₂ evolution	66 times higher than CdS	2020	[131]
Co_1.4Ni_0.6P	H₂ evolution	H₂ evolution rate of 405 µmol h^-1 g^-1	2020	[132]
PdAg/g-C₃N₄	Dehydrogenation of formic acid	TOF of 420 h^-1	2019	[133]
CdS/Ti₃C₂	H₂ evolution	7 times higher than CdS	2020	[134]
CdS/Cd	H₂ evolution	40 times compared to pure CdS	2019	[135]
Pd/SiC	Coupling of iodobenezene and phenylboronic acid	A high turnover frequency of 1053 h^-1 and a selectivity of nearly 100%	2015	[126]
Ag/Ag₂O	MO degradation	84%, 78% and 88% of MO are degraded under UV, visible and NIR irradiation	2016	[136]
CoP/g-C₃N₄	H₂ evolution	The 2D/2D structure performs 2.1 times better than 0D/2D structure	2018	[137]
Ru/TiO₂	Aerobic oxidation of benzyl alcohol	84% of MO degraded for 25 min	2016	[138]
Ag/CeO₂	MB degradation	95.33% of MB degraded within 30 min	2015	[139]
Pd/BiFeO₃	MO degradation	10.7 times higher than BiFeO₃	2016	[140]
CQDs/H-γ-TaON	H₂ evolution	H₂ evolution rate of 496.5 µmol h^-1	2015	[141]
1T‐MoS₂/CdS	H₂ evolution	39 times higher than pure CdS	2016	[142]
CdS/Cd	H₂ evolution	H₂ evolution rate of 1.68 mmol h^-1	2015	[31]
1T-MoS₂/O-g-C₃N₄ 2D	H₂ evolution	H₂ evolution rate of 1841.72 μmol h^-1 g^-1	2018	[143]
Ni/NiTe₂	H₂ evolution	A rate of 2214.2 μmol g^-1 h^-1	2020	[144]
Ag/CN	H₂ evolution	H₂ evolution rate of 364.6 μmol g^-1	2019	[145]
Ag₂WO₄/Ti₃C₂	Degradation of TC and SFE	Degradation rate of 62.9% and 88.6%, respectively	2019	[146]
Bi/Bi₂O₂CO₃	MB degradation	Complete degradation within 60 min	2016	[147]
Pt/PbS	H₂ evolution	14.38 times higher than PbS	2017	[148]

Heterojunction	Application	Performance	Year	Ref.
V₂O₅/g-C₃N₄	RhB degradation	7.3 and 13.0 times higher than individual g-C₃N₄ and V₂O₅	2016	[154]
Bi₂Fe₄O₉/Bi₂WO₆	RhB degradation	Complete degradation within 90 min	2018	[155]
Ag₂CrO₄/GO	MB degradation	3.5 times higher than Ag₂CrO₄	2015	[156]
TiO₂/CdS	CO₂ reduction	3.5 and 5.4 times higher than CdS and TiO₂	2019	[157]
BP/Bi₂WO₆	H₂ generation	9.15 times that of pristine	2019	[158]
ZnO/CeO₂	RhB degradation	2.5 and 1.7 times than pristine ZnO and CeO₂	2018	[159]
CdS/α-Fe₂O₃	H₂ generation	H₂ production rate of 45 mmol h^-1 g^-1 and high quantum efficiency of 46.9%	2020	[160]
CdS/g‐C₃N₄	H₂ generation	H₂ production rate of 15.3 mmol g^-1 h^-1	2020	[161]
WO₃(H₂O)_0.333/Ag₃PO₄	MB degradation	Complete degradation in 4 min	2019	[162]
g-C₃N₄/C-TiO₂	RhB degradation	150 times higher than TiO₂	2019	[163]
WO₃/g-C₃N₄	H₂ generation	H₂ production rate of 982 μmol h^-1 g^-1	2019	[58]
g-C₃N₄/Ag₃VO₄	MB degradation	Degradation rate of 99.3% within 8 min	2019	[164]
SnFe₂O₄/ZnFe₂O₄	Tetracycline degradation	93.2% removal efficiency	2020	[165]
Ni₂P-SNO/CdS-D	Hydrogen production	Hydrogen production rate of 7808 μmol g^-1 h^-1	2020	[166]
BiOBr/Bi₂MoO₆	Degradation of RhB	66.7% total organic carbon could be removed	2017	[167]
Bi₂S₃/Pg-C₃N₄	MB degradation	29.74 times greater than Bi₂S₃	2019	[168]
g-C₃N₄/SnS₂	CO₂ reduction	CH₃OH yield of 2.3 μmol g^-1 and CH₄ yield of 0.64 μmol g^-1	2017	[169]
WO₃/g-C₃N₄	TC degradation	Degradation rate of 90.54% within 120 min	2020	[170]
Pg-C₃N₄/Zn_0.2Cd_0.8S	H₂ generation	hydrogen production rate of 6.69 mmol g^-1 h^-1	2020	[171]
Ag₃VO₄/BiVO₄	Photocatalytic reduction of Cr⁶⁺ and oxidation of Bisphenol S	Photocatalytic reduction and oxidation efficiency of 74.9% and 94.8%	2019	[172]
LaCoO₃/g-C₃N₄	Phenol degradation	7.5 times higher than g-C₃N₄	2019	[173]
Cd_0.5Zn_0.5S/g-C₃N₄	Dye degradation	13 times higher than g-C₃N₄	2020	[174]
NiO/BiOI	RhB degradation	8 times higher than NiO	2020	[175]
Bi₂S₃/BiFeO₃	TC degradation	6 times higher than Bi₂S₃	2020	[176]

Heterojunction	Application	Performance	Year	Ref.
TiO₂(001)/(101) (101)/(001)	H₂ production	H₂ evolution rate of 264 μmol h^-1	2016	[184]
TiO₂(001)/(101)	Reduction CO₂ to CH₄	CH₄ production rate of 1.58 μmol h^-1 g^-1	2016	[186]
TiO₂(001)/(101)	Removing Hg⁰	87% Hg⁰ removal efficiency	2017	[187]
TiO₂(001)/(101)	Anti-bacteria	50% decrease in the bacterial viability in 6 h	2017	[188]
Rutile TiO₂(111)/(101)	H₂ production	0.566 mmol g^-1 h^-1H₂production rate in pure water	2019	[190]
18-facet SrTiO₃(001)/(110)	Water splitting	Fivefold enhancement of AQE than 6-facet SrTiO₃	2016	[193]
ZnGa₂O₄(110)/(111)	H₂ production	12.5 mmol g^-1 h^-1H₂production rate	2017	[194]
CaCu₃Ti₄O₁₂(001)/(111)	TC degradation	70 times higher than defect free CaCu₃Ti₄O₁₂	2019	[195]
m-BiVO₄(010)/(110)	O₂ evolution	Higher than plate-like BiVO₄	2016	[196]
BiOI(001)/(110)	MO degradation	71.4% MO degradation efficiency	2018	[197]
anatase TiO₂(001)/(101)/SnS₂	MB degradation	1.5 times better than pure TiO₂	2017	[198]
anatase TiO₂(001)/(101)/ZnS	MB degradation	2 times better than pure TiO₂	2017	[199]
BiVO₄(010)/(110)	RhB degradation	53.8% degradation efficiency within 180 min	2018	[200]
In₂O₃ loaded BiVO₄(010)/(110)	RhB degradation	91% degradation efficiency within 180 min	2017	[201]
anatase TiO₂(001)/(101)	H₂ production	a generation rate of 670 μmol h^-1 g^-1	2016	[202]
CdS loaded TiO₂(001)/(101)	4-CP degradation	96.12% degradation efficiency	2018	[203]
anatase TiO₂(001)/(101)	CO₂ Reduction	21 times increasement	2014	[181]

Heterojunction	Type	Application	Performance	Year	Ref.
BiVO₄/G/ZnSe	Z-Scheme	Water splitting	9 times higher than ZnSe	2019	[209]
CsPbBr₃/GO	Schottky	CO₂ reduction	A rate of 23.7 μmol/g h with a selectivity over 99.3%	2017	[210]
BiFeO₃/rGO	Schottky	MB degradation	Complete degradation within 100 min	2018	[211]
Ag₂CrO₄/g-C₃N₄/GO	S-Scheme	CO₂ reduction	1.5 times higher than Ag₂CrO₄/g-C₃N₄	2018	[213]
TiO₂/rGO	Schottky	RhB degradation	A rate of 53.27% within 300 min	2017	[217]
rGO/ZnO	Schottky	RhB degradation	A rate of 99.6% within 180 min	2017	[218]
GO QD/TiO₂	Type II	H₂ evolution	100 μmol h^-1	2017	[219]
(BiO)₂CO₃/BiO_2-x/graphene	Z-Scheme	Removal of NO	2 times higher than (BiO)₂CO₃	2019	[220]
ZnIn₂S₄/G	Schottky	H₂ evolution	A rate of 40.85 μmol g^-1 h^-1	2020	[221]
TiO2/rGO-EDA	Schottky	H₂ evolution	A rate of 224.9 μmol g^-1 h^-1	2020	[222]
MoS₂/N-doped G	S-Scheme	Degradation of NH₃	A degradation efficiency of 99.5% in 8 h	2020	[223]
N-TiO₂/N-doped G	Type II	MB degradation	A degradation efficiency of 87.9% within 180 min	2016	[224]
Cu₂O/G/TNA	Type II	CO₂ conversion	Methanol yield of 45 μmol cm^-2 h^-1	2016	[225]
P25/Ag₃PO₄/GO	Schottky	RhB degradation	75% degradation efficiency within 1 h	2015	[226]
TiO₂/rGO/WO₃	Z-Scheme	Disinfection	97.3 ± 3.8% of E. coli inactivation within 80 mins	2017	[227]
ZnO/g-C₃N₄/rGO	Type II	MB degradation	99.5% degradation efficiency within 15 min	2015	[228]
ZnO/MoS₂/RGO	S-Scheme	H₂ evolution	H₂ production rate of 28.616 mmol h^-1 g_cat^-1	2017	[229]
Cd_0.5Zn_0.5S/g-C₃N₄/RGO	S-Scheme	H₂ evolution	H₂ production rate of 39.24 mmol g^-1 h^-1	2018	[230]
ZnO/GQD	Type II	MB degradation	95% degradation within 70 min	2018	[231]
GQD/AgVO₃	Type II	IBP degradation	5 times higher than AgVO₃	2016	[232]
NaTaO₃/g-C₃N₄/G	Type II	MB degradation	99% removal of RhB within 70 min	2019	[233]
CdS/WS₂/graphene	Schottky	H₂ evolution	H₂ production rate of 1842 μmol g^-1 h^-1	2016	[234]
TiO_2-_x/rGO	Schottky	H₂ production	H₂ production rate of 16 mmol g^-1 h^-1	2016	[235]

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