Thermodynamic and Kinetic Influence of Oxygen Vacancies on the Solar Water Oxidation Reaction of α-Fe<sub>2</sub>O<sub>3</sub> Photoanodes
Qian Yang, Jinyan Du, Jie Li, Yuting Wu, Yong Zhou, Yang Yang, Dingming Yang, Huichao He
Abstract
To reveal the role of oxygen vacancies in the solar water oxidation of α-Fe2O3 photoanodes, the kinetic and thermodynamic properties that are closely related to the water oxidation reaction of the α-Fe2O3 photoanode containing oxygen vacancies were investigated. Compared with the pristine α-Fe2O3 photoanode, the presence of surface oxygen vacancies can improve the water oxidation activity and stability of the α-Fe2O3 photoanode simultaneously, but the bulk oxygen vacancies have a negative effect on the water oxidation performance of the α-Fe2O3 photoanode. In thermodynamics, our investigations revealed that the presence of surface oxygen vacancies narrows the space charge region width of the α-Fe2O3 photoanode, which could boost the charge separation and transfer efficiency of the α-Fe2O3 photoanode during water oxidation. Because the surface property and hydrophilicity of α-Fe2O3 are modified owing to the presence of surface oxygen vacancies, the water oxidation kinetics of the α-Fe2O3 photoanode with surface oxygen vacancies is obviously boosted. Our findings in the present work provide comprehensive understanding of the thermodynamic and kinetic differences for α-Fe2O3 photoanodes with and without oxygen vacancies for solar water oxidation.