文献类型：期刊文献

英文题名：Structural and Composition Evolution of Palladium Catalyst for CO Oxidation under Steady-State Reaction Conditions

作者：Wu, Jiawei[1,2];Chen, Dingming[1,2];Chen, Jianfu[1,2];Wang, Haifeng[1,2]

机构：[1]East China Univ Sci & Technol, Ctr Computat Chem, Key Labs Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China

年份：2023

卷号：127

期号：13

起止页码：6262

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20231413833565);WOS:【SCI-EXPANDED(收录号:WOS:000956250800001)】；

基金：This project was supported by National Key R&D Program of China (2021YFA1500700 and 2018YFA0208602), NSFC (92045303, 91945302 and 21873028), and the Fundamental Research Funds for the Central Universities. Jiawei Wu thanks the China Scholarship Council for sponsorship.

语种：英文

外文关键词：Catalyst activity - Catalytic oxidation - Genetic algorithms - Machine learning - Single crystals - Surface reactions

摘要：Understanding how the composition and structure of heterogeneous catalysts change during in situ reaction is of critical importance but greatly challenging because of the complexity of multiple time-space scale. Herein, we propose a self-adaptive simulation strategy driven by the first-principles microkinetic modeling and genetic algorithm-based global structural search accelerated by machine learning that allows the interplay of surface reaction and catalyst evolution, and uncover the structural/compositional evolution of a Pd(111) single crystal catalyst under the reaction conditions for CO oxidation, which is a classic open problem lasting for decades. The possible active phases at the kinetically steady state are identified and their common nature is unraveled. We show that, in the presence of CO/O2 reaction mixtures, a dynamically stable partially oxidized nonstoichiometric palladium oxide (PdO0.44layer) grown on Pd(111) is formed with the O adatoms inserted into the Pd(111) sublayer that drives the formation of the surface oxide. Remarkably, the first-principles microkinetic analyses demonstrate that this self-evolved PdO0.44 surface at the steady state exhibits higher catalytic activity for CO oxidation as compared with Pd(111) and overoxidized PdO catalyst, which may explain the long-standing puzzle of the "PdOx" active phase for Pd catalyst during CO oxidation.