Vanadium Cluster Neutrals Reacting with Water: Superatomic Features and Hydrogen Evolution in a Fishing Mode

Hydrogen evolution reaction (HER) is known as the heart of various energy storage and conversation systems of renewable energy sources. Here we observe the cluster reactions of a light transition metal, vanadium, with water in a gas-phase flow tube reactor. While HER products of V₁ and V₂ were not observed, the effective HER of water on neutral V (n ≥ 3) clusters reveals reasonable and size-dependent reactivity of the vanadium clusters. Superatomic features and reaction dynamics of V₁₀, V₁₃, and V₁₆ are highlighted. Among the three typical superatoms, V₁₀ and V₁₆ exhibit an abnormal superatomic orbital energy level order, 1S|2S|1P|1D..., where the energy-reduced 2S orbital helps to accommodate the geometric structure and hence reinforce the cluster stability. In comparison, V₁₃ bears a less symmetrical structure and reacts readily with water, allowing for recombination of a hydroxyl atom with an adsorbed hydrogen atom, akin to a fishing-mode HER process. The joint experimental and theoretical study on neutral V clusters clarifies the availability of superatom chemistry for transition metals and appeals further development of cluster theory based on electronic cloud/orbital analysis instead of simply counting the valence electrons. Also, we provide insights into the HER mechanism of metal clusters and propose a strategy to design new materials for portable fuel cells of hydrogen energy.