Zhou Yansong, Chen Gang, Yu Yaoguang, Feng Yujie, Zheng Yi, He Fang, Han Zhonghui
Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001, P. R. China.
Phys Chem Chem Phys. 2015 Jan 21;17(3):1870-6. doi: 10.1039/c4cp03736g. Epub 2014 Dec 4.
Reducing the oxidative capacity of holes (h(+)) in the valence band (VB) of ZnS is one of the most effective ways to prevent the photocatalyst from photocorrosion. In this work, ZnS doped only with nitrogen was prepared for the first time by nitriding ZnS powder in an NH3 atmosphere. We demonstrate theoretically and experimentally that the valence band maximum (VBM) rises obviously by N-doping in ZnS, suggesting the reduction of the oxidative capacity of holes (h(+)) in the valence band. The theoretically predicted band structures were further verified by valence band X-ray photoelectron spectroscopy (VB XPS) and Mott-Schottky measurements. The as-prepared N-doped ZnS exhibited an outstanding stable capability for photocatalytic hydrogen evolution from water under simulated sunlight irradiation for 12 h. However, pristine ZnS showed no capability and was seriously photocorroded under the same conditions.
降低硫化锌（ZnS）价带（VB）中空穴（h(+)）的氧化能力是防止光催化剂发生光腐蚀的最有效方法之一。在本工作中，首次通过在NH3气氛中对ZnS粉末进行氮化制备了仅掺杂氮的ZnS。我们通过理论和实验证明，ZnS中的N掺杂使价带最大值（VBM）明显升高，这表明价带中空穴（h(+)）的氧化能力降低。价带X射线光电子能谱（VB XPS）和莫特-肖特基测量进一步验证了理论预测的能带结构。所制备的N掺杂ZnS在模拟太阳光照射下12小时内表现出从水中光催化析氢的出色稳定能力。然而，原始的ZnS在相同条件下没有表现出能力并且严重发生了光腐蚀。
