Citation: SHANGGUAN Peng-Peng, TONG Shao-Ping, LI Hai-Li, LENG Wen-Hua. Influence of the Potential on the Charge-Transfer Rate Constant of Photooxidation of Water over α-Fe₂O₃ and Ti-Doped α-Fe₂O₃[J]. Acta Physico-Chimica Sinica, ;2013, 29(09): 1954-1960. doi: 10.3866/PKU.WHXB201306261 shu

Influence of the Potential on the Charge-Transfer Rate Constant of Photooxidation of Water over α-Fe₂O₃ and Ti-Doped α-Fe₂O₃

1.
1 College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, P. R. China;
2 Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China

Received Date: 22 April 2013
Available Online: 26 June 2013
Fund Project: 国家重点基础研究发展规划项目(973)(2011CB936003) (973)(2011CB936003)国家自然科学基金(50971116)资助 (50971116)

It has been reported that applying a certain external anodic potential over un-doped (α-Fe₂O₃) and Ti-doped α-Fe₂O₃ (Ti-Fe₂O₃) electrodes can improve the photocurrent or the photoelectrochemical oxidation rate of water. However, it is assumed in the literature that the potential drops completely across the side of the solid semiconductor (band edge pinning), and the influence of the potential on the interfacial charge-transfer rate constant is rarely reported. In this article, the impact of the applied potential on the interfacial charge-transfer rate constant during photoelectrochemical oxidation of water over the two electrodes was investigated by electrochemical impedance spectroscopy. The results showed that by increasing the applied anodic potential, the interfacial charge-transfer rate constants for both electrodes were increased. The smaller increase in the magnitude of the rate constant than determined by theory indicates that not all of the applied potential drops across the Helmholtz layer, but takes place in both the space charge and Helmholtz layers simultaneously (Fermi level pinning). The results of the surface-state capacitance measurements suggested that the photo-generated charge can be accumulated in the surface states, resulting in the re-distribution of the potential at the interface and an improvement in the rate constant. Under the same applied potential, the higher the light intensity is, the more the photogenerated holes accumulated in the surface states. This causes an increase in the potential drop across the Helmholtz layer and consequently increases the charge-transfer rate constant. Compared with the α-Fe₂O₃, the improvement of the charge-transfer rate constant by the anodic potential is more obvious.
- α-Fe₂O₃,
- Ti-doped α-Fe₂O₃,
- Photoelectrochemical oxidation of water,
- Potential distribution,
- Electrochemical impedance spectroscopy,
- Photoelectrochemistry
1. [1]
  
  (1) Fujishima, A.; Honda, K. Nature 1972, 238, 37. doi: 10.1038/238037a0
2. [2]
  (2) Esswein, M. J.; Nocera, D. G. Chem. Rev. 2007, 107, 4022. doi: 10.1021/cr050193e
3. [3]
  (3) 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
4. [4]
  (4) Zou, Z.; Ye, J.; Sayama, K.; Arakawa, H. Nature 2001, 414,625. doi: 10.1038/414625a
5. [5]
  (5) Abe, R.; Higashi, M.; Domen, K. J. Am. Chem. Soc. 2010, 132,11828. doi: 10.1021/ja1016552
6. [6]
  (6) Jin, T.; Xu, D.; Diao, P.; Xiang, M. Acta Phys. -Chim. Sin. 2012,28, 2276. [金涛,许頔,刁鹏,项民.物理化学学报,2012, 28, 2276.] doi: 10.3866/PKU.WHXB201209101
7. [7]
  (7) Du, W. P.; Li, Z.; Leng, W. H.; Xu, Y. M. Acta Phys. -Chim. Sin.2009, 25, 1530. [杜卫平,李臻,冷文华, 许宜铭.物理化学学报, 2009, 25, 1530.] doi: 10.3866/PKU.WHXB20090736
8. [8]
  (8) Glasscock, J. A.; Barnes, P. R. F.; Plumb, I. C.; Savvides, N.J. Phys. Chem. C 2007, 111, 16477. doi: 10.1021/jp074556l
9. [9]
  (9) Kay, A.; Cesar, I.; Grätzel, M. J. Am. Chem. Soc. 2006, 128,15714. doi: 10.1021/ja064380l
10. [10]
  (10) Klahr, B.; Gimenez, S.; Fabregat-Santia , F.; Bisquert, J.;Hamann, T. W. J. Am. Chem. Soc. 2012, 134, 16693. doi: 10.1021/ja306427f
11. [11]
  (11) Barroso, M.; Cowan, A. J.; Pendlebury, S. R.; Grätzel, M.; Klug,D. R.; Durrant, J. R. J. Am. Chem. Soc. 2011, 133, 14868. doi: 10.1021/ja205325v
12. [12]
  (12) Hamann, T. W. Dalton Trans. 2012, 41, 7830. doi: 10.1039/c2dt30340j
13. [13]
  (13) Wang, G.; Ling, Y.;Wheeler, D. A.; George, K. E. N.; Horsley,K.; Heske, C.; Zhang, J. Z.; Li, Y. Nano Lett. 2011, 11, 3503.doi: 10.1021/nl202316j
14. [14]
  (14) Kleiman-Shwarsctein, A.; Hu, Y. S.; Forman, A. J.; Stucky, G.D.; McFarland, E. W. J. Phys. Chem. C 2008, 112, 15900. doi: 10.1021/jp803775j
15. [15]
  (15) Liu, Y.; Yu, Y. X.; Zhang, W. D. Electrochim. Acta 2012, 59,121. doi: 10.1016/j.electacta.2011.10.051
16. [16]
  (16) Hu, Y. S.; Kleiman-Shwarsctein, A.; Stucky, G. D.; McFarland,E. W. Chem. Commun. 2009, 2652.
17. [17]
  (17) Le Formal, F.; Tetreault, N.; Cornuz, M.; Moehl, T.; Grätzel, M.;Sivula, K. Chem. Sci. 2011, 2, 737. doi: 10.1039/c0sc00578a
18. [18]
  (18) Zhang, M.; Luo, W.; Zhang, N.; Li, Z.; Yu, T.; Zou, Z.Electrochem. Commun. 2012, 23, 41. doi: 10.1016/j.elecom.2012.06.040
19. [19]
  (19) Kim, J. Y.; Jang, J. W.; Youn, D. H.; Kim, J. Y.; Kim, E. S.; Lee,J. S. RSC Adv. 2012, 2, 9415. doi: 10.1039/c2ra21169f
20. [20]
  (20) Upul-Wijayantha, K. G.; Saremi-Yarahmadi, S.; Peter, L. M.Phys. Chem. Chem. Phys. 2011, 13, 5264. doi: 10.1039/c0cp02408b
21. [21]
  (21) Leng, W. H.; Zhang, Z.; Zhang, J. Q.; Cao, C. N. J. Phys. Chem. B 2005, 109, 15008. doi: 10.1021/jp051821z
22. [22]
  (22) Cheng, X. F.; Leng, W. H.; Liu, D. P.; Xu, Y. M.; Zhang, J. Q.;Cao, C. N. J. Phys. Chem. C 2008, 112, 8725. doi: 10.1021/jp7097476
23. [23]
  (23) Oskam, G.; Schmidt, J. C.; Hoffmann, P. M.; Searson, P. C.J. Electrochem. Soc. 1996, 143, 2531. doi: 10.1149/1.1837043
24. [24]
  (24) Oskam, G.; Hoffmann, P. M.; Searson, P. C. Phys. Rev. Lett.1996, 76, 1521. doi: 10.1103/PhysRevLett.76.1521
25. [25]
  (25) Li, W.; Leng, W. H.; Niu, Z. J.; Li, X.; Fei, H.; Zhang, J. Q.;Cao, C. N. Acta Phys. -Chim. Sin. 2009, 25, 2427. [李文,冷文华,牛振江, 李想, 费会, 张鉴清,曹楚南. 物理化学学报, 2009, 25, 2427.] doi: 10.3866/PKU.WHXB20091210
26. [26]
  (26) Klahr, B.; Gimenez, S.; Fabregat-Santia , F.; Hamann, T.;Bisquert, J. J. Am. Chem. Soc. 2012, 134, 4294. doi: 10.1021/ja210755h
27. [27]
  (27) Leng, W. H.; Zhang, Z.; Cheng, S. A.; Zhang, J. Q.; Cao, C. N.Chin. Chem. Lett. 2001, 12, 1019.
28. [28]
  (28) Shangguan, P.; Tong, S.; Li, H.; Leng, W. RSC Advances 2013,3, 10163. doi: 10.1039/c3ra41439f
1. [1]
  Xinpeng LIU , Liuyang ZHAO , Hongyi LI , Yatu CHEN , Aimin WU , Aikui LI , Hao HUANG . Ga₂O₃ coated modification and electrochemical performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1105-1113. doi: 10.11862/CJIC.20230488
2. [2]
  Ru SONG , Biao WANG , Chunling LU , Bingbing NIU , Dongchao QIU . Electrochemical properties of stable and highly active PrBa_0.5Sr_0.5Fe_1.6Ni_0.4O_5+δ cathode material. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 639-649. doi: 10.11862/CJIC.20240397
3. [3]
  Pengcheng Yan , Peng Wang , Jing Huang , Zhao Mo , Li Xu , Yun Chen , Yu Zhang , Zhichong Qi , Hui Xu , Henan Li . Engineering Multiple Optimization Strategy on Bismuth Oxyhalide Photoactive Materials for Efficient Photoelectrochemical Applications. Acta Physico-Chimica Sinica, 2025, 41(2): 100014-. doi: 10.3866/PKU.WHXB202309047
4. [4]
  Qin ZHU , Jiao MA , Zhihui QIAN , Yuxu LUO , Yujiao GUO , Mingwu XIANG , Xiaofang LIU , Ping NING , Junming GUO . Morphological evolution and electrochemical properties of cathode material LiAl_0.08Mn_1.92O₄ single crystal particles. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1549-1562. doi: 10.11862/CJIC.20240022
5. [5]
  Linbao Zhang , Weisi Guo , Shuwen Wang , Ran Song , Ming Li . Electrochemical Oxidation of Sulfides to Sulfoxides. University Chemistry, 2024, 39(11): 204-209. doi: 10.3866/PKU.DXHX202401009
6. [6]
  Hongyi LI , Aimin WU , Liuyang ZHAO , Xinpeng LIU , Fengqin CHEN , Aikui LI , Hao HUANG . Effect of Y(PO₃)₃ double-coating modification on the electrochemical properties of Li[Ni_0.8Co_0.15Al_0.05]O₂. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1320-1328. doi: 10.11862/CJIC.20230480
7. [7]
  Qingtang ZHANG , Xiaoyu WU , Zheng WANG , Xiaomei WANG . Performance of nano Li₂FeSiO₄/C cathode material co-doped by potassium and chlorine ions. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1689-1696. doi: 10.11862/CJIC.20240115
8. [8]
  Ping Ye , Lingshuang Qin , Mengyao He , Fangfang Wu , Zengye Chen , Mingxing Liang , Libo Deng . 荷叶衍生多孔碳的零电荷电位调节实现废水中电化学捕集镉离子. Acta Physico-Chimica Sinica, 2025, 41(3): 2311032-. doi: 10.3866/PKU.WHXB202311032
9. [9]
  Meiqing Yang , Lu Wang , Haozi Lu , Yaocheng Yang , Song Liu . Recent Advances of Functional Nanomaterials for Screen-Printed Photoelectrochemical Biosensors. Acta Physico-Chimica Sinica, 2025, 41(2): 100018-. doi: 10.3866/PKU.WHXB202310046
10. [10]
  Yuanchao LI , Weifeng HUANG , Pengchao LIANG , Zifang ZHAO , Baoyan XING , Dongliang YAN , Li YANG , Songlin WANG . Effect of heterogeneous dual carbon sources on electrochemical properties of LiMn_0.8Fe_0.2PO₄/C composites. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 751-760. doi: 10.11862/CJIC.20230252
11. [11]
  Haojie Duan , Hejingying Niu , Lina Gan , Xiaodi Duan , Shuo Shi , Li Li . Reinterpret the heterogeneous reaction of α-Fe₂O₃ and NO₂ with 2D-COS: The role of SDS, UV and SO₂. Chinese Chemical Letters, 2024, 35(6): 109038-. doi: 10.1016/j.cclet.2023.109038
12. [12]
  Jiahong ZHENG , Jingyun YANG . Preparation and electrochemical properties of hollow dodecahedral CoNi₂S₄ supported by MnO₂ nanowires. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1881-1891. doi: 10.11862/CJIC.20240170
13. [13]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . 碳修饰的铜催化剂实现安培级电流电化学还原CO₂制C₂₊产物. Acta Physico-Chimica Sinica, 2025, 41(3): 2404012-. doi: 10.3866/PKU.WHXB202404012
14. [14]
  Shuhui Li , Xucen Wang , Yingming Pan . Exploring the Role of Electrochemical Technologies in Everyday Life. University Chemistry, 2025, 40(3): 302-307. doi: 10.12461/PKU.DXHX202406059
15. [15]
  Zihan Lin , Wanzhen Lin , Fa-Jie Chen . Electrochemical Modifications of Native Peptides. University Chemistry, 2025, 40(3): 318-327. doi: 10.12461/PKU.DXHX202406089
16. [16]
  Cailiang Yue , Nan Sun , Yixing Qiu , Linlin Zhu , Zhiling Du , Fuqiang Liu . A direct Z-scheme 0D α-Fe₂O₃/TiO₂ heterojunction for enhanced photo-Fenton activity with low H₂O₂ consumption. Chinese Chemical Letters, 2024, 35(12): 109698-. doi: 10.1016/j.cclet.2024.109698
17. [17]
  Zhihuan XU , Qing KANG , Yuzhen LONG , Qian YUAN , Cidong LIU , Xin LI , Genghuai TANG , Yuqing LIAO . Effect of graphene oxide concentration on the electrochemical properties of reduced graphene oxide/ZnS. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1329-1336. doi: 10.11862/CJIC.20230447
18. [18]
  Liangzhen Hu , Li Ni , Ziyi Liu , Xiaohui Zhang , Bo Qin , Yan Xiong . A Green Chemistry Experiment on Electrochemical Synthesis of Benzophenone. University Chemistry, 2024, 39(6): 350-356. doi: 10.3866/PKU.DXHX202312001
19. [19]
  Cen Zhou , Biqiong Hong , Yiting Chen . Application of Electrochemical Techniques in Supramolecular Chemistry. University Chemistry, 2025, 40(3): 308-317. doi: 10.12461/PKU.DXHX202406086
20. [20]
  Yongming Zhu , Huili Hu , Yuanchun Yu , Xudong Li , Peng Gao . Construction and Practice on New Form Stereoscopic Textbook of Electrochemistry for Energy Storage Science and Engineering: Taking Basic Course of Electrochemistry as an Example. University Chemistry, 2024, 39(8): 44-47. doi: 10.3866/PKU.DXHX202312086

Get Citation

PDF

XML

Metrics

PDF Downloads(680)
Abstract views(758)
HTML views(6)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Influence of the Potential on the Charge-Transfer Rate Constant of Photooxidation of Water over α-Fe2O3 and Ti-Doped α-Fe2O3

Metrics

通讯作者: 陈斌, bchen63@163.com

Influence of the Potential on the Charge-Transfer Rate Constant of Photooxidation of Water over α-Fe₂O₃ and Ti-Doped α-Fe₂O₃