期刊
JOURNAL OF MATERIALS CHEMISTRY A
卷 10, 期 22, 页码 11948-11954出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1ta08889k
关键词
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资金
- National Natural Science Foundation of China (NFSC) [21890380, 21272285]
- Natural Science Foundation of Guangdong Province [2021A1515010132]
A metallacycle-based porous crystal was synthesized for selective electroconversion of CO2 to CH4. The metallacycle module features open metal sites and can act as a nano-reactor to mimic enzymatic cavity, enabling high selectivity in CO2 conversion.
There is a growing interest in designing electrocatalysts for highly selective electroreduction of CO2 to deeply reduced products such as CH4. However, CO2-to-CH4 conversion remains a great challenge in controlling the multi-electron/proton transfer and the adsorption of key intermediates. In this work, a metallacycle-based porous crystal (1) was synthesized for selective CO2-to-CH4 electroconversion in aqueous solution. The single-crystal analysis results disclosed that the metallacycle module of 1 features open metal sites and could be self-adaptive to encapsulate guest molecules of different sizes in its cavity. These enable the metallacycle to function as a nano-reactor to mimic the enzymatic cavity that is surrounded by catalytically active sites and adaptively bind to diverse substrates and intermediates. Accordingly, 1 exhibits desirable CO2 capture capacity, and its porous framework further promotes CO2 diffusion to catalytic sites. The above merits bring about an excellent CH4 selectivity of 70% with a partial current density of 10.3 mA cm(-2) in a H-type cell at -1.5 V (versus the reversible hydrogen electrode), while a CH4 selectivity up to 81% with a partial current density of 23 mA cm(-2) in a flow cell. Mechanistic investigations suggested that the adaptive cavity and the synergistic effect of aromatic hydrogen atoms, via hydrogen-bonding interactions, are beneficial to stabilize the key intermediates of CO2-to-CH(4 )conversion. This work develops a novel platform to regulate the reactivity and selectivity of CO2 electroreduction reactions.
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