Fu Cong, Li Fei, Wu Zongfang, Xiong Feng, Zhu Junfa, Gong Xue-Qing, Huang Weixin
Key Laboratory of Precision and Intelligent Chemistry, iChEM, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China.
Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China.
J Phys Chem Lett. 2023 Oct 12;14(40):8916-8921. doi: 10.1021/acs.jpclett.3c02047. Epub 2023 Sep 28.
Reconstruction of solid surfaces is generally accompanied by changes in surface activities. Here, via a combined experimental and theoretical study, we successfully identified that a trace amount of potassium dopant restructures the mineral anatase TiO(001) single-crystal surface from an added molecule (ADM) termination to an added oxygen (AOM) one without changing the (1×4) periodicity. The anatase TiO(001)-(1×4)-ADM surface terminated with 4-fold coordinated Ti and 2-fold coordinated O sites is (photo)catalytically active, whereas the anatase TiO(001)-(1×4)-AOM surface terminated with O and inaccessible 5-fold coordinated Ti sites is inert. These results unveiled a mechanism of dopant-induced transformation from a reactive to an inert TiO(001)-(1×4) surface, which unifies the existing arguments about the surface structures and (photo)catalytic activity of anatase TiO(001)-(1×4).
固体表面的重构通常伴随着表面活性的变化。在此，通过实验与理论相结合的研究，我们成功确定，微量的钾掺杂剂可将矿物锐钛矿TiO(001)单晶表面从添加分子（ADM）终止结构转变为添加氧（AOM）终止结构，而不改变(1×4)周期性。以4配位Ti和2配位O位点终止的锐钛矿TiO(001)-(1×4)-ADM表面具有（光）催化活性，而以O和难以接近的5配位Ti位点终止的锐钛矿TiO(001)-(1×4)-AOM表面是惰性的。这些结果揭示了掺杂剂诱导的从活性TiO(001)-(1×4)表面到惰性表面转变的机制，统一了关于锐钛矿TiO(001)-(1×4)表面结构和（光）催化活性的现有观点。
