Liu Tianhui, Peng Tianze, Fu Bina, Zhang Dong H
School of Sciences, Great Bay University, Songshan Lake International Innovation Entrepreneurship Community A5, Dongguan 523000, China.
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
J Phys Chem Lett. 2023 Nov 2;14(43):9713-9719. doi: 10.1021/acs.jpclett.3c02556. Epub 2023 Oct 25.
Understanding polar molecule dynamics on bimetallic surfaces, especially electropositivity and electronegativity, remains a challenge. Here, we report the reactivity of HCl on a strained Ag monolayer on Au(111) using six-dimensional quantum dynamics with a new machine-learning-based potential energy surface. Surprisingly, HCl reactivity is significantly suppressed by the Ag-Au interaction despite a lower HCl+Ag/Au(111) barrier than pure Ag(111). This arises from charge transfer between Ag and Au, where electronegative Au makes the top Ag layer on Ag/Au(111) electropositive, unlike that on pure Ag(111). Electropositive Ag in HCl+Ag/Au(111) attracts Cl, yielding an unfavorable H-Cl configuration and reduced reactivity. These findings deepen our understanding of polar molecule interactions on bimetallic surfaces, highlighting the role of charge transfer in dissociative chemisorption and the implications for catalyst design in heterogeneous catalysis.
理解双金属表面上的极性分子动力学，尤其是电正性和电负性，仍然是一项挑战。在此，我们使用基于机器学习的新势能面，通过六维量子动力学报告了HCl在Au(111)上的应变Ag单层上的反应活性。令人惊讶的是，尽管HCl+Ag/Au(111)的势垒比纯Ag(111)低，但Ag-Au相互作用显著抑制了HCl的反应活性。这源于Ag和Au之间的电荷转移，其中电负性的Au使Ag/Au(111)上的顶层Ag层呈电正性，这与纯Ag(111)上的情况不同。HCl+Ag/Au(111)中的电正性Ag吸引Cl，产生不利的H-Cl构型并降低反应活性。这些发现加深了我们对双金属表面上极性分子相互作用的理解，突出了电荷转移在解离化学吸附中的作用以及对多相催化中催化剂设计的影响。
