文献类型：期刊文献

英文题名：Origin of Chemisorption Energy Scaling Relations over Perovskite Surfaces

作者：Li, Yang[1];Cheng, Wei[1];Sui, Zhi-Jun[1];Zhou, Xing-Gui[1];Chen, De[2];Yuan, Wei-Kang[1];Zhu, Yi-An[1]

机构：[1]East China Univ Sci & Technol, United Chem React Engn Res Inst UNILAB, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]Norwegian Univ Sci & Technol, Dept Chem Engn, N-7491 Trondheim, Norway

年份：2019

卷号：123

期号：46

起止页码：28275

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20194707710734);WOS:【SCI-EXPANDED(收录号:WOS:000499737700030)】；

基金：This work is supported by the Natural Science Foundation of China (nos. 21473053, 91645122, and U1663221), the National Key Research and Development Program of China (no. 2018YFB0604700), and the Fundamental Research Funds for the Central Universities (no. 222201718003). The computational time provided by the Notur project is highly acknowledged.

语种：英文

外文关键词：Catalysis - Catalysts - Metal ions - Precious metals - Barium compounds - Positive ions - Chemisorption - Oxygen vacancies - Ionic strength - Electronic structure - Oxygen - Strontium compounds

摘要：Rationally tailored perovskites ABO(3) are promising substitutes for expensive noble-metal catalysts in heterogeneous catalysis. In this contribution, the BEEF-vdW + U method has been used to examine the adsorption of H, C, O, and CH3 over (K,Rb,Cs,Sr,Ba)BO3 (B = d-block transition metals) and ARuO(3) (A = La to Ho) with various crystal structures. The calculated chemisorption energy of the simple species at the O site scales well with the surface oxygen vacancy formation energy of all the perovskites under consideration, while the trend in the chemisorption energy at the B site can be described by the surface metal vacancy formation energy only over ARuO(3). Electronic structure analysis indicates that the perovskites could be classified into several categories according to the splitting and filling of the d and f orbitals of the B- and A-site cations, respectively. In each category, the chemisorption energies at the B site on (K,Rb,Cs,Sr,Ba)BO3 and ARuO(3) are also closely related to the strength of the ionic bonding in the perovskites. Hence, the surface oxygen vacancy formation energy can be used as a descriptor to explain the trend in the calculated adsorption energies upon substitution of either B- or A-site cations, which has its origin in the fact that the larger the actual partial charges the oxygen and transition-metal ions carry, the stronger the B-O bond, which in turn weakens and enhances the ability of the O anions to withdraw and the ability of the B cations to donate electrons to the adsorbates, respectively.