Molecular hydrogen is one of the essential reactants in the chemical industry, and its generation from renewable sources such as biomass materials and water is of great benefit to the future society. Generally, molecular oxygen should be pre-eliminated in the hydrogen evolution reactions (HERs) in order to avoid the reverse hydrogen oxidation reaction (HOR). Here, we report a highly efficient HER from a formaldehyde/water mixture using MgO supported Ag nanoparticles (AgNPs/MgO) as the catalyst and molecular oxygen as a promoter. The HER rate depends almost linearly on the oxygen partial pressure, and the optimal turnover frequency (TOF) of the silver catalyst exceeds 6,600 h–1. Based on the experimental and theoretical results, a surface stabilized MgO/Ag–•OOH complex is suggested to be the main catalytically active species for the HER.

A unique tandem catalytic system by coupling H2 production with organic dye degradation is achieved by hollow PdO.

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.

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