Engineering surface states of hematite based photoanodes for boosting photoelectrochemical water splitting

Hematite-based photoanodes are promising candidates for photoelectrochemical water splitting. However, the performance of pristine hematite semiconductors is unsatisfactory due to charge recombination occurring at different interfaces: back contact, bulk and semiconductor/electrolyte interfaces. Increasing efforts have been focused on enhancing the performance of hematite based photoanodes via nanostructure control, doping, heterojunction construction, and surface modification with a secondary semiconductor or an oxygen evolution electrocatalyst. Most of the previous studies attributed the enhanced PEC water splitting performance to the changes in the donor density via doping, the formation of type II heterojunction via a secondary semiconductor coating and the improved water oxidation kinetics via coating oxygen evolution electrocatalysts. However, the role of surface states presented at the semiconductor/electrolyte interfaces of hematite-based photoanodes has been overlooked in previous investigations, which virtually play a critical role in determining the photoelectrochemical water oxidation process. In this review, we summarize the recent progress of various techniques employed for the detection of surface states of hematite photoanodes and highlight the important role of modifying surface states in the development of high performance hematite based photoanodes for photoelectrochemical water splitting application. The challenges and future prospects in the study of hematite based photoanodes are also discussed.