ISSN 1000-6818CN 11-1892/O6CODEN WHXUEU
Acta Phys Chim Sin >> 2016,Vol.32>> Issue(1)>> 2-13     doi: 10.3866/PKU.WHXB201510192         中文摘要
On the Importance of Surface Reactions on Semiconductor Photocatalysts for Solar Water Splitting
CHANG Xiao-Xia, GONG Jin-Long
Collaborative Innovation Center of Chemical Science and Engineering, Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, P. R. China
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One of the most appealing ways to resolve the worldwide energy crisis and environmental pollution is by converting solar energy into storable chemical energy as hydrogen through solar water splitting. The redox reactions of photogenerated charge carriers occurring on the surface of photocatalysts during the process of solar water splitting are particularly complex. Owing to the high reaction overpotentials and sluggish desorption kinetics of gas products, surface reaction is the rate-determining step in the solar water splitting process. Therefore, a great deal of attention has been focused on this specific research area. The recent advances and prospects for future directions regarding the importance of surface reactions for solar water splitting are presented. The main strategies to enhance the surface water splitting reaction kinetics are summarized. The roles and classifications of surface cocatalysts, as well as the effects of passivating the surface states and coating surface protective layers, are discussed by integrating the principles of photocatalysis. Prospects for the future development of surface reaction research are also proposed.

Keywords: Photocatalytic water splitting   Surface reaction   Photocatalyst   Cocatalyst   Surface state   Protective layer  
Received: 2015-09-01 Accepted: 2015-10-19 Publication Date (Web): 2015-10-19
Corresponding Authors: GONG Jin-Long Email:

Fund: The project was supported by the National Natural Science Foundation of China (U1463205, 21222604, 51302185, 21525626).

Cite this article: CHANG Xiao-Xia, GONG Jin-Long. On the Importance of Surface Reactions on Semiconductor Photocatalysts for Solar Water Splitting[J]. Acta Phys. -Chim. Sin., 2016,32 (1): 2-13.    doi: 10.3866/PKU.WHXB201510192

(1) Osterloh, F. E. Chem. Soc. Rev. 2013, 42, 2294. doi: 10.1039/C2CS35266D
(2) Das, D.; Veziroglu, T. N. Int. J. Hydrog. Energy 2001, 26, 13. doi: 10.1016/S0360-3199(00)00058-6
(3) Fujishima, A.; Honda, K. Nature 1972, 238, 37. doi: 10.1038/238037a0
(4) Kudo, A.; Miseki, Y. Chem. Soc. Rev. 2009, 38, 253. doi: 10.1039/B800489G
(5) Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; Mi, Q.; Santori, E. A.; Lewis, N. S. Chem. Rev. 2010, 110, 6446. doi: 10.1021/cr1002326
(6) Kubacka, A.; Fernández-García, M.; Colón, G. Chem. Rev. 2012, 112, 1555. doi: 10.1021/cr100454n
(7) Ran, J. R.; Zhang, J.; Yu, J. G.; Jaroniec, M.; Qiao, S. Z. Chem. Soc. Rev. 2014, 43, 7787. doi: 10.1039/C3CS60425J
(8) Valdés, Á.; Brillet, J.; Grätzel, M.; Gudmundsdóttir, H.; Hansen, H. A.; Jónsson, H.; Klüpfel, P.; Kroes, G.; Le Formal, F.; Man, I. C.; Martins, R. S.; Nörskov, J. K.; Rossmeisl, J.; Sivula, K.; Vojvodic, A.; Zäch, M. Phys. Chem. Chem. Phys. 2012, 14, 49. doi: 10.1039/C1CP23212F
(9) Hope, G. A.; Bard, A. J. J. Phys. Chem. 1983, 87, 1979. doi: 10.1021/j100234a029
(10) Wu, N. L.; Lee, M. S. Int. J. Hydrog. Energy 2004, 29, 1601. doi: 10.1016/j.ijhydene.2004.02.013
(11) Tran, P. D.; Xi, L.; Batabyal, S. K.; Wong, L. H.; Barber, J.; Loo, J. S. C. Phys. Chem. Chem. Phys. 2012, 14, 11596. doi: 10.1039/c2cp41450c
(12) Lin, K. Y.; Ma, B. J.; Su, W. G.; Liu, W. Y. Science & Technology Review 2013, 31, 103. [林克英, 马保军, 苏暐光, 刘万毅. 科技导报, 2013, 31, 103.]
(13) Yamaguti, K.; Sato, S. J. Chem. Soc. Faraday Trans. 1 1985, 81, 1237. doi: 10.1039/f19858101237
(14) Abe, R.; Sayama, K.; Arakawa, H. Chem. Phys. Lett. 2003, 371, 360. doi: 10.1016/S0009-2614(03)00252-5
(15) Maeda, K.; Teramura, K.; Lu, D.; Saito, N.; Inoue, Y.; Domen, K. Angew. Chem. 2006, 118, 7970.
(16) Li, Y. H.; Xing, J.; Chen, Z. J.; Li, Z.; Tian, F.; Zheng, L. R.; Wang, H. F.; Hu, P.; Zhao, H. J.; Yang, H. G. Nat. Commun. 2013, 4, 2500.
(17) Zong, X.; Han, J.; Ma, G.; Yan, H.; Wu, G.; Li, C. J. Phys. Chem. C 2011, 115, 12202.
(18) Sun, D. S.; Fu, B. Y.; Yang, W. L.; Wang, H. M.; Tian, M. K. Applied Chemical Industry 2015, 44, 720. [孙懂山, 付伯艳, 杨万亮, 王会敏, 田蒙奎. 应用化工, 2015, 44, 720.]
(19) Xiang, Q.; Yu, J.; Jaroniec, M. J. Am. Chem. Soc. 2012, 134, 6575. doi: 10.1021/ja302846n
(20) Artero, V.; Chavarot-Kerlidou, M.; Fontecave, M. Angew. Chem. Int. Edit. 2011, 50, 7238. doi: 10.1002/anie.v50.32
(21) Sato, J.; Saito, N.; Yamada, Y.; Maeda, K.; Takata, T.; Kondo, J. N.; Hara, M.; Kobayashi, H.; Domen, K.; Inoue, Y. J. Am. Chem. Soc. 2005, 127, 4150. doi: 10.1021/ja042973v
(22) Kanan, M. W.; Nocera, D. G. Science 2008, 321, 1072. doi: 10.1126/science.1162018
(23) Zhong, D. K.; Choi, S.; Gamelin, D. R. J. Am. Chem. Soc. 2011, 133, 18370. doi: 10.1021/ja207348x
(24) Liao, M.; Feng, J.; Luo, W.; Wang, Z.; Zhang, J.; Li, Z.; Yu, T.; Zou, Z. Adv. Funct. Mater. 2012, 22, 3066. doi: 10.1002/adfm.v22.14
(25) Kim, T. W.; Choi, K. S. Science 2014, 343, 990. doi: 10.1126/science.1246913
(26) Maeda, K.; Lu, D.; Domen, K. Chemistry 2013, 19, 4986. doi: 10.1002/chem.201300158
(27) Lee, R.; Tran, P. D.; Pramana, S. S.; Chiam, S. Y.; Ren, Y.; Meng, S.; Wong, L. H.; Barber, J. Catal. Sci. Technol. 2013, 3, 1694. doi: 10.1039/c3cy00054k
(28) Wang, D.; Hisatomi, T.; Takata, T.; Pan, C.; Katayama, M.; Kubota, J.; Domen, K. Angew. Chem. Int. Edit. 2013, 52, 11252. doi: 10.1002/anie.v52.43
(29) Li, R.; Zhang, F.; Wang, D.; Yang, J.; Li, M.; Zhu, J.; Zhou, X.; Han, H.; Li, C. Nat. Commun. 2013, 4, 1432. doi: 10.1038/ncomms2401
(30) Klahr, B.; Gimenez, S.; Fabregat-Santiago, F.; Hamann, T.; Bisquert, J. J. Am. Chem. Soc. 2012, 134, 4294. doi: 10.1021/ja210755h
(31) Formal, F. L.; Tétreault, N.; Cornuz, M.; Moehl, T.; Grätzel, M.; Sivula, K. Chem. Sci. 2011, 2, 737. doi: 10.1039/C0SC00578A
(32) Hwang, Y. J.; Hahn, C.; Liu, B.; Yang, P. ACS Nano 2012, 6, 5060. doi: 10.1021/nn300679d
(33) Zandi, O.; Hamann, T. W. J. Phys. Chem. Lett. 2014, 5, 1522. doi: 10.1021/jz500535a
(34) Lee, M. H.; Takei, K.; Zhang, J.; Kapadia, R.; Zheng, M.; Chen, Y. Z.; Nah, J.; Matthews, T. S.; Chueh, Y. L.; Ager, J. W.; Javey, A. Angew. Chem. Int. Edit. 2012, 51, 10760. doi: 10.1002/anie.v51.43
(35) Wang, T.; Gong, J. Angew. Chem. Int. Edit. 2015, 54, 2. doi: 10.1002/anie.201410932
(36) Hu, S.; Shaner, M. R.; Beardslee, J. A.; Lichterman, M.; Brunschwig, B. S.; Lewis, N. S. Science 2014, 344, 1005. doi: 10.1126/science.1251428
(37) Li, C.; Wang, T.; Luo, Z.; Zhang, D.; Gong, J. Chem. Commun. 2015, 51, 7290. doi: 10.1039/C5CC01015B
(38) Bard, A. J.; Fox, M. A. Accounts Chem. Res. 1995, 28, 141. doi: 10.1021/ar00051a007
(39) Trotochaud, L.; Mills, T. J.; Boettcher, S. W. J. Phys. Chem. Lett. 2013, 4, 931. doi: 10.1021/jz4002604
(40) Morales-Guio, C. G.; Mayer, M. T.; Yella, A.; Tilley, S. D.; Grätzel, M.; Hu, X. J. Am. Chem. Soc. 2015, 137, 9927. doi: 10.1021/jacs.5b05544
(41) Zhong, M.; Hisatomi, T.; Kuang, Y.; Zhao, J.; Liu, M.; Iwase, A.; Jia, Q.; Nishiyama, H.; Minegishi, T.; Nakabayashi, M.; Shibata, N.; Niishiro, R.; Katayama, C.; Shibano, H.; Katayama, M.; Kudo, A.; Yamada, T.; Domen, K. J. Am. Chem. Soc. 2015, 137, 5053. doi: 10.1021/jacs.5b00256
(42) Chang, X.; Wang, T.; Zhang, P.; Zhang, J.; Li, A.; Gong, J. J. Am. Chem. Soc. 2015, 137, 8356. doi: 10.1021/jacs.5b04186
(43) Liu, J.; Liu, Y.; Liu, N.; Han, Y.; Zhang, X.; Huang, H.; Lifshitz, Y.; Lee, S. T.; Zhong, J.; Kang, Z. Science 2015, 347, 970. doi: 10.1126/science.aaa3145
(44) Barroso, M.; Pendlebury, S. R.; Cowan, A. J.; Durrant, J. R. Chem. Sci. 2013, 4, 2724. doi: 10.1039/c3sc50496d
(45) Werner, D.; Furube, A.; Okamoto, T.; Hashimoto, S. J. Phys. Chem. C 2011, 115, 8503. doi: 10.1021/jp112262u

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2. FENG Chang, DENG Xiao-Yan, NI Xiao-Xiao, LI Wei-Bing.Fabrication of Carbon Dots Modified Porous ZnO Nanorods with Enhanced Photocatalytic Activity[J]. Acta Phys. -Chim. Sin., 2015,31(12): 2349-2357
3. GUO Zhang-Long, HUANG Li-Qiong, CHU Wei, LUO Shi-Zhong.Effects of Promoter on NiMgAl Catalyst Structure and Performance for Carbon Dioxide Reforming of Methane[J]. Acta Phys. -Chim. Sin., 2014,30(4): 723-728
4. DU Shu-Qing, YUAN Yu-Feng, TU Wei-Xia.Microwave-Hydrothermal Synthesis and Photocatalytic Activity of Zn2GeO4 Nanoribbons[J]. Acta Phys. -Chim. Sin., 2013,29(09): 2062-2068
5. SHANG Yang, CHEN Yang, SHI Zhan-Bin, ZHANG Dong-Feng, GUO Lin.Synthesis and Visible Light Photocatalytic Activities of Au/Cu2O Heterogeneous Nanospheres[J]. Acta Phys. -Chim. Sin., 2013,29(08): 1819-1826
6. YUAN Wen-Hui, LIU Xiao-Chen, LI Li.Improving Photocatalytic Performance for Hydrogen Generation over Co-Doped ZnIn2S4 under Visible Light[J]. Acta Phys. -Chim. Sin., 2013,29(01): 151-156
7. ZHENG Hua-Rong, ZHANG Jin-Shui, WANG Xin-Chen, FU Xian-Zhi.Modification of Carbon Nitride Photocatalysts by Copolymerization with Diaminomaleonitrile[J]. Acta Phys. -Chim. Sin., 2012,28(10): 2336-2342
8. CHEN Xiao-Yun, LU Dong-Fang, HUANG Jin-Feng, LU Yan-Feng, ZHENG Jian-Qiang.Preparation and Properties of N-F Co-Doped TiO2 Photocatalyst with Wide Range Light Response and Multipore Structure from Ionic Liquid-Water Mixture Solvent[J]. Acta Phys. -Chim. Sin., 2012,28(01): 161-169
9. LI Ben-Xia, WANG Yan-Fen, LIU Tong-Xuan.Adjustable Synthesis and Visible-Light Responsive Photocatalytic Performance of V2O5·xH2O-BiVO4 Nanocomposites[J]. Acta Phys. -Chim. Sin., 2011,27(12): 2946-2952
10. LU Sheng-Yong, HUANG Yi-Long, WANG Qiu-Lin, LI Xiao-Dong, YAN Jian-Hua.Photocatalytic Degradation of Gaseous 1,2-Dichlorobenzene over TiO2/AC Photocatalysts[J]. Acta Phys. -Chim. Sin., 2011,27(09): 2191-2199
11. YING Hong, WANG Zhi-Yong, GUO Zheng-Duo, SHI Zu-Jin, YANG Shang-Feng.Reduced Graphene Oxide-Modified Bi2WO6 as an Improved Photocatalyst under Visible Light[J]. Acta Phys. -Chim. Sin., 2011,27(06): 1482-1486
12. XIAO Lixin, DUAN Laiqiang, CHAI Junyi, WANG Yun, CHEN Zhijian, QU Bo, GONG Qihuang.Fabrication of Large Area of Anodic Aluminum Oxide Ultrathin Film Directly onto an ITO Electrode with a Ti Buffer Layer[J]. Acta Phys. -Chim. Sin., 2011,27(03): 749-753
13. ZHANG Ai-Ping, ZHANG Jin-Zhi.Syntheses and Activities of Visible-Light-Driven Cu/BiVO4 Composite Photocatalysts[J]. Acta Phys. -Chim. Sin., 2010,26(05): 1337-1342
14. FAN You-Jun, ZHEN Chun-Hua, CHEN Sheng-Pei, SUN Shi-Gang.Effect of Specific Adsorption of Anions and Surface Structure of Pt(111) Electrode on Kinetics of Dissociative Adsorption of Ethylene Glycol[J]. Acta Phys. -Chim. Sin., 2009,25(05): 999-1003
15. HU Yuan-Fang; LI Yue-Xiang; PENG Shao-Qin; LV Gong-Xuan; LI Shu-Ben.Photocatalytic Properties of Composite of SiO2 and Pt-Cd0.53Zn0.47S Solid Solutions[J]. Acta Phys. -Chim. Sin., 2008,24(11): 2071-2076
16. LI Xiao-Hui, LIU Shou-Xin.Characterization of Visible Light Response N-F Codoped TiO2 Photocatalyst Prepared by Acid Catalyzed Hydrolysis[J]. Acta Phys. -Chim. Sin., 2008,24(11): 2019-2024
17. CHEN Yu-Juan; HU Zhong-Hua; WANG Xiao-Jing; ZHAO Guo-Hua; LIU Ya-Fei; LIU Wei.Influence of Pore Size and Surface Area of Activated Carbon on the Performance of TiO2/AC Photocatalyst[J]. Acta Phys. -Chim. Sin., 2008,24(09): 1589-1596
18. LIU Fu-Sheng; JI Ren; WU Min; SUN Yue-Ming.Hydrogen Production from Water Splitting Using Perylene Dye-Sensitized Pt/TiO2 Photocatalyst[J]. Acta Phys. -Chim. Sin., 2007,23(12): 1899-1904
19. LI Hong-Jian; CHEN Gang; LI Zhong-Hua; ZHOU Chao.Synthesis and Photocatalytic Decomposition of Water under Visible Light Irradiation of La2Ti2-xCoxO7 with Pyrochlore Structure[J]. Acta Phys. -Chim. Sin., 2007,23(05): 761-764
20. CHEN Xiao-Yun; LIU Shou-Xin.Preparation and Characterization of S-doped Ti1-xSyO2 Photocatalyst withWide Range Light Response[J]. Acta Phys. -Chim. Sin., 2007,23(05): 701-708
21. FANG Shu-Mei; OU Yan; LIN Jing-Dong; LIAO Dai-Wei.Preparation of Cu/Sr3Ti2O7 and Its Photocatalytic Activity of Watersplitting for Hydrogen Evolution[J]. Acta Phys. -Chim. Sin., 2007,23(04): 601-604
22. TIAN Meng-Kui; JIANG Li; SHANGGUAN Wen-Feng; WANG Shi-Jie2;OUYANG Zi-Yuan.Electronic Structures of the Visible-light Driven Photocatalysts K4Ce2Ta10O30, K4Ce2Nb10O30 and Their Solid Solution Compounds[J]. Acta Phys. -Chim. Sin., 2007,23(04): 466-472
23. CHEN Xiao-Yun;LIU Shou-Xin;CHEN Xi;SUN Cheng-Lin.Characterization and Activity of TiO2 /wAC Composite Photocatalyst Prepared by Acid Catalyzed Hydrolysis Method[J]. Acta Phys. -Chim. Sin., 2006,22(05): 517-522
24. LIN Wei; ZHANG Yong-fan; LI Yi; CHEN Yong; LI Jun-qian.First Principle Studies on the Geometry and Electronic Structures of the SnO2(110) Surface[J]. Acta Phys. -Chim. Sin., 2006,22(01): 76-81
25. Xu Xin;Lü Xin;Wang Nan-Qin;Zhang Qian-Er.Cluster Modeling of Chemisorption and Reactions on Metal Oxide Surfaces[J]. Acta Phys. -Chim. Sin., 2004,20(08S): 1045-1054
26. Fan You-Jun;Fan Chun-Jie;Zhen Chun-Hua;Chen Sheng-Pei;Sun Shi-Gang.Kinetics of Dissociative Adsorption of Ethylene Glycol on Pt(111) Electrode[J]. Acta Phys. -Chim. Sin., 2004,20(04): 382-385
27. Zhang Jin-Long;Zhao Wen-Juan;Chen Hai-Jun;Xu Hua-Sheng;Chen Ai-Ping;Anpo Masa-Kazu.Study of Loaded Photocatalysts by Precious Metals on the Photocatalytic Reactivity[J]. Acta Phys. -Chim. Sin., 2004,20(04): 424-427
28. Ruan Sheng-Ping;Wang Jing;Zhang Li;Yang Dong;Xuan Li.Effects of Surface State of Nanocrystal PbTiO3 on Their Dielectric Properties[J]. Acta Phys. -Chim. Sin., 2003,19(07): 593-596
29. Zhang Yong-Fan;Li Jun-Qian;Ding Kai-Ning;Chen Wen-Kai;Zhou Li-Xin.Theoretical Studies on the Geometries and Electronic Structures of the (111) Surfaces of Transition-Metal Carbides[J]. Acta Phys. -Chim. Sin., 2003,19(01): 40-45
30. Zhong Shun-He;Chen Song-Zhe;Xin Xiu-Lan.Laser Stimulated Surface Reaction of C2H4 on Nickel Sulfate[J]. Acta Phys. -Chim. Sin., 2001,17(10): 936-939
31. Xue Jun;Zhu Jian-Hua;Shen Bin;Ma Li-Li.Investigation on Catalytic Decomposition of N-nitrosamines over Zeolites[J]. Acta Phys. -Chim. Sin., 2001,17(08): 696-701
32. Nan Xiao-Lin;Zhang Jin;Liu Zhong-Fan;Shi Zu-Jin;Gu Zhen-Nan.Patterned Assembly of Shortened SingleWalled Carbon Nanotubes on Gold Surface[J]. Acta Phys. -Chim. Sin., 2001,17(05): 393-396
33. Tao Yue-Wu;Zhong Shun-He.Laser Stimulated Isobutane Selective Oxidation Reaction on the Surface of Li and Bi Mixed Phosphate[J]. Acta Phys. -Chim. Sin., 2001,17(04): 356-360
34. Zhong Shun-He, Gao Feng, Ye Xiu-Qiang, Xiao Xiu-Fen.Study on Laser Stimulated Surface Reaction of Methanol Oxidative Coupling[J]. Acta Phys. -Chim. Sin., 2000,16(07): 601-607
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