期刊
ACS CATALYSIS
卷 6, 期 12, 页码 8276-8285出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.6b02613
关键词
water oxidation; photocatalysis; BiOCl; oxygen vacancies; facet dependence
资金
- National Natural Science Funds for Distinguished Young Scholars [21425728]
- National Basic Research Program of China (973 Program) [2013CB632402]
- National Key Research and Development Program of China [2016YFA0203002]
- National Science Foundation of China [51472100]
- Self-Determined Research Funds of CCNU from the Colleges' Basic Research and Operation of MOE [CCNU14Z01001, CCNU16A02029]
- Central China Normal University [2015YBZD018, 2016YBZZ034]
A central issue in understanding photocatalytic water splitting on a stoichiometric or defective nanostructured oxide surface is its adsorption mode and related reactivity. More than just improving the adsorption of water on oxide surfaces, we demonstrate in this work that surface oxygen vacancies (OVs) also offer a possibility of activating water toward thermodynamically enhanced photocatalytic water oxidation, while the water activation state, as reflected by its capability to trap holes, strongly depends on the structures of OVs. Utilizing well-ordered BiOCl single-crystalline surfaces, we reveal that dissociatively adsorbed water on the OV of the (010) surface exhibits higher tendency to be oxidized than the molecularly adsorbed water on the OV of the (001) surface. Analysis of the geometric atom arrangement shows that the OV of the BiOCl (010) surface can facilitate barrierless O-H bond breaking in the first proton removal reaction, which is sterically hindered on the OV of the BiOCl (001) surface, and also allow more localized electrons transfer from the OV to the dissociatively adsorbed water, leading to its higher water activation level for hole trapping. These findings highlight the indispensable role of crystalline surface structure on water oxidation and may open up avenues for the rational design of highly efficient photocatalysts via surface engineering.
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