Spectroscopic identification of water splitting by neutral group 3 metals

Spectroscopic study of water splitting by neutral metal clusters is crucial to understanding the microscopic mechanism of catalytic processes but has been proven to be a challenging experimental target due to the difficulty in size selection. Here, we report a size-specific infrared spectroscopic study of the reactions between neutral group 3 metals and water molecules based on threshold photoionization using a vacuum ultraviolet laser. Quantum chemical calculations were carried out to identify the structures and to assign the experimental spectra. All the M2O4H4 (M = Sc, Y, La) products are found to have the intriguing M2(μ2-O)(μ2-H)(μ2-OH)(η1-OH)2 structures, indicating that the HOH bond breaking, the MO/MH/MOH bond formation, and hydrogen production proceed efficiently in the reactions between laser-vaporized metals and water molecules. The joint experimental and theoretical results on the atomic scale demonstrate that the water splitting by neutral group 3 metals is both thermodynamically exothermic and kinetically facile in the gas phase. These findings have important implications for unravelling the structure-reactivity relationship of catalysts with isolated metal atoms/clusters dispersed on supports. Spectroscopic study of water splitting by neutral metal clusters is extremely challenging due to the difficulty in size selection. Herein, the novel M2O4H4 (M = Sc, Y, La) complexes are characterized to have the intriguing M2(μ2-O)(μ2-H)(μ2-OH)(η1-OH)2 structures by infrared spectroscopy, revealing that the HOH bond breaking, the MO/MH/MOH bond formation, and hydrogen production proceed efficiently in the reactions between laser-vaporized metals and water molecules. [Display omitted]