Citation: YAO Li-Zhen, KONG De-Sheng, DU Jiu-Yao, WANG Ze, ZHANG Jing-Wei, WANG Na, LI Wen-Juan, FENG Yuan-Yuan. Enhancement of the Photoelectrochemical Activity of α-Fe₂O₃ Materials by Surface Modification with Vanadium[J]. Acta Physico-Chimica Sinica, ;2015, 31(10): 1895-1904. doi: 10.3866/PKU.WHXB201509074 shu

Enhancement of the Photoelectrochemical Activity of α-Fe₂O₃ Materials by Surface Modification with Vanadium

1.
Department of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong Province, P. R. China

Received Date: 10 July 2015
Available Online: 7 September 2015
Fund Project: 山东省自然科学基金(ZR2010EM026) (ZR2010EM026)国家级大学生创新创业训练计划项目(201410446044)资助 (201410446044)

Surface modification of semiconductor materials is an effective way to improve their photocatalysis and photo-conversion activities. Bare and V-modified α-Fe₂O₃ photoelectrode materials were prepared using hydrothermal, chemical bath deposition and heat treatment approaches. Their physicochemical and photoelectrochemical (PEC) properties were then investigated with X-ray diffractometry (XRD), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), voltammetry, and electrochemical AC impedance spectroscopy (EIS) techniques. The existence of FeVO4 was indicated by its characteristic X-ray diffractometry patterns, while no significant red shifts in the photoabsorption edge were detected in UV-Vis diffuse reflectance spectroscopy spectra. With V-modified and bare Fe₂O₃ serving as a photoanode, photoelectrochemical measurements were carried out for water splitting in 1 molmol·L^-1 NaOH (pH 13.6). The enhancement of α-Fe₂O₃ photoelectrochemical activities through V-modification was indicated by significantly increased photocurrents and decreased photocharge-recombination probability. By measuring electrochemical AC impedance spectroscopy spectra, pseudo-first-order rate constants for the charge transfer at the illuminated electrode/solution interface were estimated. The rate constant for V-modification of the Fe₂O₃ electrode was higher than that of the bare Fe₂O₃ electrode. Improved interfacial charge transfer kinetics through V-modification is responsible for the enhanced photoelectrochemical activities of α-Fe₂O₃. The interfacial photocharge transfer and recombination processes and their properties are discussed with a semiconductor energy band model constructed for the electrode system.
- Water splitting,
- Interfacial charge transfer,
- Surface recombination,
- Photocurrent,
- AC impedance spectroscopy
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Enhancement of the Photoelectrochemical Activity of α-Fe₂O₃ Materials by Surface Modification with Vanadium