文献类型：期刊文献

英文题名：Molecular Adsorption Kinetics: Nonlinear Entropy-Enthalpy Loss Quantified by Constrained AIMD and Insights into the Adsorption-Site Determination on Metal Oxides

作者：Peng, Chao[1,2,3,4];Chen, Jianfu[1,2];Hu, Peijun[1,2,5];Wang, Haifeng[1,2]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, Ctr Computat Chem, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[3]Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Hunan, Peoples R China;[4]Chinese Acad Sci, Multiscale Crystal Mat Res Ctr, Shenzhen Inst Adv Technol, Shenzhen 518055, Peoples R China;[5]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, Antrim, North Ireland

年份：2021

卷号：125

期号：20

起止页码：10974

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20212110410089);WOS:【SCI-EXPANDED(收录号:WOS:000657357100016)】；

基金：This project was supported by National Key R&D Program of China (2018YFA0208602), NSFC (21873028, 91945302, 21703067, and 92045303), National Ten Thousand Talent Program for Young Top-Notch Talents in China, Shanghai ShuGuang project (17SG30), the Fundamental Research Funds for the Central Universities, and the Natural Science Foundation of Hunan Province (2019JJ50526, 200SZK023, and 2020JJ5470).

语种：英文

外文关键词：Free energy - Platinum compounds - Adsorption - Entropy - Catalysis - Cobalt compounds - Molecular dynamics - Temperature distribution - Catalyst activity - Metals - Rhodium compounds

摘要：Quantifying the molecular adsorption/ desorption rate is vital in ascertaining the catalytic activity/mechanism but falls far short of expectations, limited by the explicit description of the elusive entropy effect. Herein, we quantitatively unravel the free energy barriers of adsorption/desorption steps at specific temperatures by the state-of-the-art constrained molecular dynamic simulations, with the origin traced to the delicate entropy-enthalpy interplay; the augmented loss of entropy caused by minor enthalpy drops leads to an adsorption barrier, while the desorption barrier is largely determined by the enthalpy cost. As an example, the long-term adsorption-site puzzle of a CO molecule on metal oxide is resolved-the Co3+ on Co3O4(110) is the adsorption site instead of the lattice O2- that is found to be a reacting site. Notably, it is proved that the obtained barriers on Co3+ differ with any traditional estimation method and show an interesting linear temperature dependence. Generally, we explore the CO adsorption barriers on typical metal surfaces (Cu, Rh, Pd, Ag, Pt, and Au) and find a good scaling with the adsorption energies. We believe that these insights could deepen the fundamental understanding of adsorption/desorption kinetics in heterogeneous catalysis and inspire studies for accurate determination of adsorption processes.