Affiliation: | 1. School of Metallurgy and Environment, Central South University, Changsha, 410083 Hunan, P.R. China Hunan Joint International Research Center for Carbon Dioxide Resource Utilization, State Key Laboratory of Powder Metallurgy, School of Physics and Electronics, Central South University, Changsha, 410083 Hunan, P.R. China;2. Hunan Joint International Research Center for Carbon Dioxide Resource Utilization, State Key Laboratory of Powder Metallurgy, School of Physics and Electronics, Central South University, Changsha, 410083 Hunan, P.R. China;3. School of Metallurgy and Environment, Central South University, Changsha, 410083 Hunan, P.R. China;4. Nanoinstitut München, Fakultät für Physik, Ludwig-Maximilians-Universität München, 80539 München, Germany;5. MOE Key Laboratory of Resource Chemistry and Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University, Shanghai, 200234 P.R. China |
Abstract: | Photoelectrochemical (PEC) water splitting is a promising approach for renewable solar light conversion. However, surface Fermi level pinning (FLP), caused by surface trap states, severely restricts the PEC activities. Theoretical calculations indicate subsurface oxygen vacancy (sub-Ov) could release the FLP and retain the active structure. A series of metal oxide semiconductors with sub-Ov were prepared through precisely regulated spin-coating and calcination. Etching X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and electron energy loss spectra (EELS) demonstrated Ov located at sub ∼2–5 nm region. Mott–Schottky and open circuit photovoltage results confirmed the surface trap states elimination and Fermi level de-pinning. Thus, superior PEC performances of 5.1, 3.4, and 2.1 mA cm−2 at 1.23 V vs. RHE were achieved on BiVO4, Bi2O3, TiO2 with outstanding stability for 72 h, outperforming most reported works under the identical conditions. |