期刊
ACS APPLIED MATERIALS & INTERFACES
卷 11, 期 37, 页码 33946-33954出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsami.9b11023
关键词
cluster; formaldehyde; reforming; hydrogen production; proton-coupled electron transfer
资金
- National Natural Science Foundation of China [21872123, 21503189, 21403197]
- Zhejiang Provincial Natural Science Foundation of China [LY18B030007, LY15B030009]
- Fundamental Research Funds of Zhejiang Sci-Tech University [2019Q005]
- Start-up Foundation of Zhejiang Sci-Tech University [16062096-Y]
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 H-2 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 pi orbital of chemisorbed bridged O-2 molecules, leading to the implementation of low-temperature O-2 adsorption and activation. The catalytically active species, (OOH)-O-center dot, is thus selectively generated via a preferential two-electron reduction of O-2 with a low energy barrier on Ag sites, involving an unusual long-range proton-coupled electron transfer process. The (OOH)-O-center dot-AgUCs/MgO active center is efficient for the subsequent C-H activation and H-2 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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