A Revealing Insight into Gold Cluster Photocatalysts: Visible versus (Vacuum) Ultraviolet Light

Jingjing Zhang; Heng-Ding Wang; Yifei Zhang; Zhiwen Li; Dongyuan Yang; Dong H Zhang; Tatsuya Tsukuda; Gao Li

doi:10.1021/acs.jpclett.3c00509

A Revealing Insight into Gold Cluster Photocatalysts: Visible versus (Vacuum) Ultraviolet Light

J Phys Chem Lett. 2023 May 11;14(18):4179-4184. doi: 10.1021/acs.jpclett.3c00509. Epub 2023 Apr 28.

Authors

Jingjing Zhang^{1

2}, Heng-Ding Wang³, Yifei Zhang^{4

1}, Zhiwen Li^{1

2}, Dongyuan Yang³, Dong H Zhang³, Tatsuya Tsukuda⁵, Gao Li^{1

2}

Affiliations

¹ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P. R. China.
² University of Chinese Academy of Sciences, Beijing 101408, China.
³ State Key Laboratory Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
⁴ Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China.
⁵ Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

PMID: 37114860
DOI: 10.1021/acs.jpclett.3c00509

Abstract

[Au₂₅(PPh₃)₁₀(SC₂H₄Ph)₅Cl₂]²⁺ (Au25) supported on TiO₂ (P25) exhibited distinct photocatalytic behaviors in the oxidation of amines using visible or ultraviolet light. The activity under visible light (455 nm) was superior to that under ultraviolet light. To gain insight into the origin of this difference, we investigated the photoreaction pathways of Au25 isolated in the gas phase upon irradiation with a pulsed laser with wavelengths of 455, 193, and 154 nm. High-resolution mass spectrometry revealed photon energy-dependent pathways for Au25: dissociation of the PPh₃ ligands and PPh₃AuCl units at 455 nm, dissociation into small [Au_nS_m]⁺ ions (n = 3-20; m = 0-4) at 193 nm, and ionization affording the triply charged state at 154 nm. These results were substantiated by density functional theory simulations. On the basis of these results, we proposed that the inferior photocatalytic activity of Au25/P25 under ultraviolet light is mainly due to the poor photostability of Au25.