文献类型：期刊文献

英文题名：Molecular-Level Insights into the Notorious CO Poisoning of Platinum Catalyst

作者：Chen, Wenyao[1];Cao, Junbo[1];Fu, Wenzhao[1];Zhang, Jing[1];Qian, Gang[1];Yang, Jia[2];Chen, De[2];Zhou, Xinggui[1];Yuan, Weikang[1];Duan, Xuezhi[1]

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

年份：2022

卷号：61

期号：16

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20220811703953);WOS:【SCI-EXPANDED(收录号:WOS:000760037200001)】；

基金：This work was financially supported by 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). The authors thank Prof. Yefei Li from Fudan University and Prof. Fan Yang from ShanghaiTech University for the help of DFT calculation and UPS analyses, respectively. The authors thank beamline BL14W1 (Shanghai Synchrotron Radiation Facility) for the beam time and assistant in the experiments.

语种：英文

外文关键词：Activation; Adsorption; CO Poisoning; Electrons; Kinetics

摘要：Carbon monoxide (CO) is notorious for its strong adsorption to poison platinum group metal catalysts in the chemical industry. Here, we conceptually distinguish and quantify the effects of the occupancy and energy of d electrons, emerging as the two vital factors in d-band theory, for CO poisoning of Pt nanocatalysts. The stepwise defunctionalization of carbon support is adopted to fine-tune the 5d electronic structure of supported Pt nanoparticles. Excluding other promotional mechanisms, the increase of Pt 5d band energy strengthens the competitive adsorption of hydrogen against CO for the preferential oxidation of CO, affording the scaling relationship between Pt 5d band energy and CO/H-2 adsorption energy difference. The decrease of Pt 5d band occupancy lowers CO site coverage to promote its association with oxygen for the total oxidation of CO, giving the scaling relationship between Pt 5d occupancy and activation energy. The above insights outline a molecular-level understanding of CO poisoning.