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 V_n⁺ (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 V_n⁺ (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.

水及其与金属的相互作用与人类生活密切相关，金属团簇与水的反应性对于理解氢的产生至关重要。 在室温下阳离子钒簇与水的反应中观察到钒簇 V _n ⁺ (3 ≤  n ≤ 30)上单个水分子的显着析氢反应 (HER) 。结合实验和理论研究表明，V-OH 基团的摇摆振动会在 V _n ⁺ ( n ≥ 3) 团簇并允许末端氢与吸附的氢原子相互作用，从而释放氢。三个金属原子的存在降低了决速步骤的能垒，从而使单个水分子有效地产生氢气。这种机制不同于多个水分子在铝簇阴离子上的解离化学吸附，后者通常通过在多个表面位点处至少两个水分子的解离化学吸附，然后吸附的氢原子重新组合来进行。