Ultrasmall Silver Clusters Stabilized on MgO for Robust Oxygen-Promoted Hydrogen Production from Formaldehyde...

Efficient molecular hydrogen generation from renewable biomass-derived resources and water is of great importance to the sustainable development of the future society. Herein, ultrasmall Ag nanoclusters supported on a defect-rich MgO matrix (AgUCs/MgO) are synthesized by a facile impregnation/calcination method and are applied to robust oxygen-promoted formaldehyde reforming into H₂ at room temperature. Density functional theory calculations and experimental observations show that the catalyst spatially builds up a channel for directional electron transfer from electron-rich Ag sites to the anti-bonding π orbital of chemisorbed bridged O₂ molecules, leading to the implementation of low-temperature O₂ adsorption and activation. The catalytically active species, ^•OOH, is thus selectively generated via a preferential two-electron reduction of O₂ with a low energy barrier on Ag sites, involving an unusual long-range proton-coupled electron transfer process. The ^•OOH-AgUCs/MgO active center is efficient for the subsequent C-H activation and H₂ generation, leading to a 3-fold improvement of the turnover frequency as compared with its analogous AgNPs/MgO catalyst. Our atomic-level design and synthetic strategy provide a platform that facilitates the construction of an electron-proton transfer channel for catalysis, altered adsorption configurations of activated reactants, and enhancement of catalytic hydrogen generation activity, extending a promising direction for the development of next-generation energy catalysts.