Interplay between H2S and Anatase TiO2(101) Surface: The Effect of Subsurface Oxygen Vacancy
Interplay between H2S and Anatase TiO2(101) Surface: The Effect of Subsurface Oxygen Vacancy
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H2S 与锐钛矿型 TiO2(101) 表面之间的相互作用：次表面氧空位的影响
DOI：
10.1021/acs.jpcc.1c09627
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Ya-Nan Tang
中科院分区：
文献类型：
--
作者：
Zhi-Wen Wang;Wei-Guang Chen;Da Teng;Jie Zhang;An-Ming Li;Zhao-Han Li;Ya-Nan Tang
用第一性原理方法研究了H2S与TiO2（101）表面氧空位的相互作用。一方面，H_2S的吸附可以逆转亚表层和表层VO的相对稳定性，使表层VO在能量上变得比亚表层VO更有利。同时，H2S的吸附也能有效地促进VO从次表层向表层的扩散。另一方面，研究结果表明，亚表层和表层VOs都能促进H2S的解离。亚表层VO能直接促进H_2S的解离。而H_2S则通过两条间接途径在表面与表面钒发生解离。具体而言，H2S在具有表面VO的表面上解离后，两个完全解离的H2S的吸附在能量上比具有亚表面VO的表面更稳定，H2S中的硫原子填充表面VO位，形成稳定的S掺杂TiO2表面.这一结论揭示了H2S与亚表面氧空位之间的本质相互作用，为揭示TiO2（101）表面光催化活性的来源提供了一种可能的途径，同时也为获得S掺杂的TiO2表面提供了一种可能的方法。
The interaction between H2S and oxygen vacancy on the anatase TiO2(101) surface has been theoretically studied by using first-principles calculations. On one hand, it is found that the relative stability of the subsurface and surfaceVOcould be reversed by H2S adsorption, and the surfaceVObecomes energetically more favorable than the subsurfaceVO. Meanwhile, the adsorption of H2S also can efficiently facilitateVOdiffusion from the subsurface layer to the surface layer. On the other hand, the results show that both the subsurface and the surfaceVOs can facilitate the H2S dissociation. SubsurfaceVOcan facilitate the H2S dissociation directly. In contrast, the H2S dissociates on the surface with surfaceVOby two indirect pathways. Specifically, after H2S dissociation on the surface with surfaceVO, the adsorption of the two complete dissociative H2S are energetically more stable than that of the surface with subsurfaceVO, and the sulfur atoms from H2S fill in the surfaceVOsite and form stable S-doped TiO2surfaces. This conclusion reveals the essential interaction between H2S and a subsurface oxygen vacancy, which may provide a possible way to illuminate the origin of the photocatalytic activity of the anatase TiO2(101) surface, and offers a possible method to obtain the S-doped TiO2surface.