Abstract Single-atom catalysts have attracted exceptional interest of researchers. However, the arguing whether tuning the interactions between the dispersed single metals and the support can enhance the activity, selectivity and stability of single atom catalysts is still open. Herein, single atom Au catalyst (rutile Au1@TiO2) is presented via density functional theory calculations, which exhibits high efficiency for methanol oxidation to formate, especially the exposed (110) facet. Rutile Au1@TiO2 (110) facet prefers to localize at 6-fold Ti site under rich-oxygen conditions; methanol goes through adsorption, O-H dissociation, C-H dissociation, O2 molecule adsorption, and withdraws H2O and formate to gas phase separately. In particular, a significant step on the way to methanol oxidation is the oxygen vacancy formation at the reduced rutile Au1@TiO2 (110) surface after C-H scission and H2O desorption. The subsequent adsorbed O2 molecule does only provide oxygen species for methanol oxidation, but not fill surface oxygen vacancy, which promotes formate formation and desorption to develop very well.

中文翻译：

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金红石 Au1@TiO2 催化剂上的甲醇氧化：晶面和氧空位的重要性

摘要 单原子催化剂引起了研究人员的极大兴趣。然而，调节分散的单金属与载体之间的相互作用是否可以提高单原子催化剂的活性、选择性和稳定性仍存在争议。在此，通过密度泛函理论计算提出了单原子 Au 催化剂（金红石 Au1@TiO2），其表现出高效的甲醇氧化成甲酸盐，尤其是暴露的（110）面。富氧条件下金红石Au1@TiO2(110)面更倾向于定位在6倍Ti位点；甲醇经过吸附、OH解离、CH解离、O2分子吸附，分别抽出H2O和甲酸盐进入气相。特别是，甲醇氧化的一个重要步骤是在 CH 断裂和 H2O 解吸后在还原的金红石 Au1@TiO2（110）表面形成氧空位。随后吸附的O2分子只为甲醇氧化提供氧物种，而没有填充表面氧空位，促进甲酸盐的形成和解吸发展得很好。