文献类型：期刊文献

英文题名：Molecular-level insights into the electronic effects in platinum-catalyzed carbon monoxide oxidation

作者：Chen, Wenyao[1];Cao, Junbo[1];Yang, Jia[2];Cao, Yueqiang[1];Zhang, Hao[3,4];Jiang, Zheng[4,5];Zhang, Jing[1];Qian, Gang[1];Zhou, Xinggui[1];Chen, De[2];Yuan, Weikang[1];Duan, Xuezhi[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]Norwegian Univ Sci & Technol, Dept Chem Engn, N-7491 Trondheim, Norway;[3]Soochow Univ, Inst Funct Nano & Soft Mat Lab FUNSOM, Jiangsu Key Lab Carbon Based Funct Mat & Devices, Suzhou 215123, Peoples R China;[4]Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai 201800, Peoples R China;[5]Chinese Acad Sci, Shanghai Adv Res Inst, Zhangjiang Lab, Shanghai Synchrotron Radiat Facil, Shanghai 201210, Peoples R China

年份：2021

卷号：12

期号：1

外文期刊名：NATURE COMMUNICATIONS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000722866700035)】；

基金：W.C., X.Z., and X.D. acknowledge funding from the Natural Science Foundation of China (21922803, 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 beamline BL14W1 (Shanghai Synchrotron Radiation Facility) for the beam time and assistant in the experiments.

语种：英文

摘要：A molecular-level understanding of how the electronic structure of metal center tunes the catalytic behaviors remains a grand challenge in heterogeneous catalysis. Herein, we report an unconventional kinetics strategy for bridging the microscopic metal electronic structure and the macroscopic steady-state rate for CO oxidation over Pt catalysts. X-ray absorption and photoelectron spectroscopy as well as electron paramagnetic resonance investigations unambiguously reveal the tunable Pt electronic structures with well-designed carbon support surface chemistry. Diminishing the electron density of Pt consolidates the CO-assisted O-2 dissociation pathway via the O*-O-C*-O intermediate directly observed by isotopic labeling studies and rationalized by density-functional theory calculations. A combined steady-state isotopic transient kinetic and in situ electronic analyses identifies Pt charge as the kinetics indicators by being closely related to the frequency factor, site coverage, and activation energy. Further incorporation of catalyst structural parameters yields a novel model for quantifying the electronic effects and predicting the catalytic performance. These could serve as a benchmark of catalyst design by a comprehensive kinetics study at the molecular level. A molecular-level understanding of the electronic effects remains a grand challenge in heterogeneous catalysis. Here, the authors report an unconventional kinetics strategy for bridging the upscaling gap between the microscopic fingerprints of active sites and the macroscopic catalytic performance.