Engineering electronic platinum-carbon support interaction to tame carbon monoxide activation  

作　　者：Wenyao Chen Changwei Liu Cheng Lian Yaxin Yu Xiangxue Zhang Gang Qian Jia Yang De Chen Xinggui Zhou Weikang Yuan Xuezhi Duan 

机构地区：[1]State Key Laboratory of Chemical Engineering,East China University of Science and Technology,130 Meilong Road,Shanghai 200237,China. [2]Department of Chemical Engineering,Norwegian University of Science and Technology,Trondheim 7491,Norway

出　　处：《Fundamental Research》2024年第5期1118-1127,共10页自然科学基础研究（英文版）

基　　金：supported by grants from the Natural Science Foundation of China(21922803,22178100,92034301,22008066,and 21776077);the China Postdoctoral Science Foundation(BX20190116);the Innovation Program of Shanghai Municipal Education Commission,the Program of Shanghai Academic/Technology Research Leader(21XD1421000);111 Project of the Ministry of Education of China(B08021);BL14W1(Shanghai Synchrotron Radiation Facility)for the beam time and assistance in the experiments.

摘　　要：CO oxidation has been studied for more than a century;however,molecular-level understanding of its activation protocol and related intermediates remains elusive.Here,we present a unified mechanistic and kinetic picture of various electronic metal-support interactions within platinum-carbon catalysts via in situ spectroscopic/kinetic analyses and multi-scale simulations.Transient kinetic analysis and molecular dynamics simulations with a reactive force field provided a quantitative description of the competition between the oxygen association and oxygen dissociation mechanisms tuned by the interfacial charge distribution and CO coverage.Steady-state isotopic transient kinetic analysis and density functional theory calculations revealed a simultaneous shift in the rate-determining step(RDS)from O_(2)^(*)dissociation to O^(*)and CO^(*)and O_(2)^(*)and CO^(*)association.A de novo strategy from the interfacial charge distribution to the reaction mechanism,kinetics/thermodynamics of RDS,and,ultimately,catalytic performance was developed to quantitatively map the above CO activation mechanism with an order-of-magnitude increase in reactivity.The proposed catalytic picture and de novo strategy are expected to prompt the development of theories and methodologies for heterogeneous catalysis.

关 键 词：CO activation EMSI Reaction pathway Rate-determining stepde novo strategy 

分 类 号：O64[理学—物理化学]