Oxygen Vacancy Structure Associated Photocatalytic Water Oxidation of BiOCl
Oxygen Vacancy Structure Associated Photocatalytic Water Oxidation of BiOCl
复制标题
氧空位结构相关的 BiOCl 光催化水氧化
DOI：
10.1021/acscatal.6b02613
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发表时间：
2016-12-01
期刊：
影响因子：
12.9
通讯作者：
Zhang, Lizhi
中科院分区：
文献类型：
--
作者：
Li, Hao;Shang, Jian;Zhang, Lizhi
理解化学计量或缺陷纳米结构氧化物表面上的光催化水分解的中心问题是其吸附模式和相关反应性。不仅仅是提高水在氧化物表面上的吸附，我们在这项工作中证明，表面氧空位（OVs）也提供了一种可能性，活化水向光催化增强的光催化水氧化，而水的活化状态，反映了其捕获空穴的能力，强烈依赖于OVs的结构。利用有序的BiOCl单晶表面，我们发现，解离吸附在OV的（010）表面上的水表现出更高的倾向被氧化比分子吸附在OV的（001）表面上的水。原子的几何排列分析表明，BiOCl（010）表面的OV能促进第一次质子去除反应中的无势垒O-H键断裂，而BiOCl（001）表面的OV对第一次质子去除反应具有空间位阻作用，这是由于BiOCl（001）表面的OV对第一次质子去除反应具有空间位阻作用。
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, a...