[2+1] Cycloadditions Modulate the Hydrophobicity of Ni-N₄ Single-Atom Catalysts for Efficient CO₂ Electroreduction

Shu, Siyan1,2,3; Song, Tao1,2,3,6; Wang, Cheng1,2,3; Dai, Hao1,2,3; Duan, Lele2,3,4,5

2024-07-15

10.1002/anie.202405650

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

Microenvironment regulation of M-N-4 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-N-4 sites through strong covalent bonding and under mild reaction conditions are highly desired. Taking the hydrophilic Ni-N-4 SAC as a representative, we report herein a [2+1] cycloaddition reaction between Ni-N-4 and in situ generated difluorocarbene (F2C:), and enable the surface fluorocarbonation of Ni-N-4, resulting in the formation of a super-hydrophobic Ni-N-4-CF2 catalyst. Meanwhile, the mild reaction conditions allow Ni-N-4-CF2 to inherit both the electronic and structural configuration of the Ni-N-4 sites from Ni-N-4. 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-N-4-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.

[2+1] cycloaddition surface functionalization single-atom catalyst microenvironment CO2 reduction

SCI ; EI

英语

第一

null[22179057]

Chemistry

Chemistry, Multidisciplinary

WOS:001243036300001

WILEY-V C H VERLAG GMBH

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Westlake Univ, Ctr Artificial Photosynth Solar Fuels, Sch Sci, Hangzhou 310024, Peoples R China
3.Westlake Univ, Sch Sci, Dept Chem, Hangzhou 310024, Peoples R China
4.Westlake Univ, Div Solar Energy Convers & Catalysis, Zhejiang Baima Lake Lab Co Ltd, Hangzhou 310000, Zhejiang, Peoples R China
5.Westlake Inst Adv Study, Inst Nat Sci, Hangzhou 310024, Peoples R China
6.Harbin Inst Technol, Sch Chem & Chem Engn, Harbin 150001, Peoples R China

Shu, Siyan,Song, Tao,Wang, Cheng,et al. [2+1] Cycloadditions Modulate the Hydrophobicity of Ni-N₄ Single-Atom Catalysts for Efficient CO₂ Electroreduction[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2024,63(29).

Shu, Siyan,Song, Tao,Wang, Cheng,Dai, Hao,&Duan, Lele.(2024).[2+1] Cycloadditions Modulate the Hydrophobicity of Ni-N₄ Single-Atom Catalysts for Efficient CO₂ Electroreduction.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,63(29).

Shu, Siyan,et al."[2+1] Cycloadditions Modulate the Hydrophobicity of Ni-N₄ Single-Atom Catalysts for Efficient CO₂ Electroreduction".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 63.29(2024).