Activation Mechanism of the H2 on Au6‐based Clusters From the Perspective of Chemical Bonding

Author:

Hu Yujie1,Zhang Manli1,Liu Qiman12ORCID

Affiliation:

1. Anhui Engineering Research Center for Photoelectrocatalytic Electrode Materials Huainan Normal University Huainan 232038 P. R. China

2. Anhui Key Laboratory of Photoelectric‐Magnetic Functional Materials Anqing Normal University Anqing 246133 P. R. China

Abstract

AbstractRecently, there is an interesting report (J. Am. Chem. Soc. 2020, 142, 13090–13101) on the photoinduced mechanism for the H2 dissociation studied through a simple Au6‐H2 model. However, the adsorption energy between the Au6 and H2 is only 0.25 eV, and the H─H bond length is only slightly longer. Based on the structural framework of the triangular Au6, we have investigated the adsorptions of H2 on the transition metals (TM = Ni, Cu, and Zn group elements) and revealed the differences in activation of H2 on TM atoms. The results confirm that the activation of H2 by the Au5Ni cluster is the best in terms of the stability and adsorption energy (0.89 eV), where the H─H stretching frequency also has a very obvious redshift compared with the free H2. The AIMD simulations show that the Au5Ni‐H2 maintains an excellent thermal stability even at 500 K. The density of states, molecular orbitals, NCI‐RDG, and bond order analyses indicate that the Ni∙∙∙H2 and Au∙∙∙H2 are rather strong, directly showing the bonding interactions. By studying H2 adsorptions on TM atoms, one can obtain fundamental insight into elementary steps that take place on catalytically active surfaces.

Publisher

Wiley

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