催化作用
化学
Atom(片上系统)
有机化学
计算机科学
嵌入式系统
作者
Siyan Shu,Tao Song,Cheng Wang,Hao Dai,Lele Duan
出处
期刊:Angewandte Chemie
[Wiley]
日期:2024-05-02
卷期号:63 (29): e202405650-e202405650
被引量:54
标识
DOI:10.1002/anie.202405650
摘要
Microenvironment regulation of M-N4 single-atom catalysts (SACs) is a promising way to tune their catalytic properties toward the electrochemical CO2 reduction reaction. However, strategies that can effectively introduce functional groups around the M-N4 sites through strong covalent bonding and under mild reaction conditions are highly desired. Taking the hydrophilic Ni-N4 SAC as a representative, we report herein a [2+1] cycloaddition reaction between Ni-N4 and in situ generated difluorocarbene (F2C:), and enable the surface fluorocarbonation of Ni-N4, resulting in the formation of a super-hydrophobic Ni-N4-CF2 catalyst. Meanwhile, the mild reaction conditions allow Ni-N4-CF2 to inherit both the electronic and structural configuration of the Ni-N4 sites from Ni-N4. Enhanced electrochemical CO2-to-CO Faradaic efficiency above 98 % is achieved in a wide operating potential window from -0.7 V to -1.3 V over Ni-N4-CF2. In situ spectroelectrochemical studies reveal that a highly hydrophobic microenvironment formed by the -CF2- group repels asymmetric H-bonded water at the electrified interface, inhibiting the hydrogen evolution reaction and promoting CO production. This work highlights the advantages of [2+1] cycloaddition reactions on the covalent modification of N-doped carbon-supported catalysts.
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