COMMUNICATIONS CHEMISTRY 3 : 148 (2020)
Hydrogen release from a single water molecule on Vn+ (3 ≤ n ≤ 30)
Hanyu Zhang1,4, Haiming Wu1,4, Yuhan Jia1,2, Baoqi Yin1,2, Lijun Geng1, Zhixun Luo1,2✉ & Klavs Hansen3
1 Beijing National Laboratory of Molecular sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P.R. China.
2 University of Chinese Academy of Sciences, Beijing 100049, P.R. China.
3 Joint Centre for Quantum Studies and Department of Physics, School of Science, Tianjin University, Tianjin, P.R. China.
4 These authors contributed equally: Hanyu Zhang, Haiming Wu. ✉email: zxluo@iccas.ac.cn
ABSTRACT
Water and its interactions with metals are closely bound up with human life, and the reactivity of metal clusters with water is of fundamental importance for the understanding of hydrogen generation. Here a prominent hydrogen evolution reaction (HER) of single water molecule on vanadium clusters Vn+ (3 ≤ n ≤ 30) is observed in the reaction of cationic vanadium clusters with water at room temperature. The combined experimental and theoretical studies reveal that the wagging vibrations of a V-OH group give rise to readily formed V-O-V intermediate states on Vn+ (n ≥ 3) clusters and allow the terminal hydrogen to interact with an adsorbed hydrogen atom, enabling hydrogen release. The presence of three metal atoms reduces the energy barrier of the rate-determining step, giving rise to an effective production of hydrogen from single water molecules. This mechanism differs from dissociative chemisorption of multiple water molecules on aluminium cluster anions, which usually proceeds by dissociative chemisorption of at least two water molecules at multiple surface sites followed by a recombination of the adsorbed hydrogen atoms.
