Covalently Hydrophobic Nanocarbon Supported Ni Single‐Atom Catalysts for Highly Selective CO <sub>2</sub> Electroreduction
Abstract
ABSTRACT Precise tailoring of hydrophobic microenvironments surrounding catalytic active sites has emerged as a critical strategy for enhancing the efficiency of electrochemical CO 2 reduction reaction. However, covalent modulation of catalyst hydrophobicity is rarely reported, and the mechanistic influence of hydrophobicity‐driven interfacial catalysis remains unclear. Herein, we report a general synthetic methodology for the covalent immobilization of structurally tunable hydrophobic alkyl chains onto nanocarbon‐loaded single‐atom catalysts. The covalently hydrophobic nanocarbon supported Ni single‐atom catalysts deliver near‐unity CO selectivity over a broad potential range from −0.5 to −1.2 V (versus the reversible hydrogen electrode) in flow cells. Integrated spectroscopic, computational kinetic, and thermodynamic analyses reveal that the alkyl chains form hydrophobic barriers by disrupting interfacial water networks, resulting in a 0.37 eV increase in energy barrier of the hydrogen evolution reaction. The hydrophobic micro‐environment further stabilizes the *COOH intermediate under aqueous conditions, lowering its formation Gibbs energy (Δ G ) by 0.17 eV relative to unmodified catalysts. This work establishes a universal hydrophobic modification strategy for carbon‐based catalysts that breaks the conventional activity‐selectivity trade‐off in aqueous electrocatalysis, opening new opportunities for optimizing gas‐consumption electrochemical reactions.
Article Details
Authors (12)
Yanzheng Ji
School of Materials Science and Engineering Southeast University Nanjing Jiangsu China
Huaizhu Wang
State Key Laboratory of Coordination Chemistry, MOE Key Laboratory of Mesoscopic Chemistry, MOE Key Laboratory of High Performance Polymer Materials and Technology, Jiangsu Key Laboratory of Advanced Organic Materials, Suzhou Key Laboratory of Green Intelligent Manufacturing of New Energy Materials and Devices, Tianchang New Materials and Energy Technologies Research Center, Institute of Green Chemistry and Engineering, School of Chemistry and Chemical Engineering
Yuxiao Meng
Key Laboratory of Quantum Materials and Devices of Ministry of Education, School of Physics
Chongyi Ling
Zhikang Cheng
School of Materials Science and Engineering Southeast University Nanjing Jiangsu China
Chunhui Liu
Xinquan Yu
School of Materials Science and Engineering Southeast University Nanjing Jiangsu China
Zuoxiu Tie
State Key Laboratory of Coordination Chemistry, MOE Key Laboratory of Mesoscopic Chemistry, MOE Key Laboratory of High Performance Polymer Materials and Technology, Jiangsu Key Laboratory of Green Energy Catalysis and Intelligent Chemical Engineering, Suzhou Key Laboratory of Green Intelligent Manufacturing of New Energy Materials and Devices, Tianchang New Materials and Energy Technologies Research Center, Institute of Green Chemistry and Engineering, School of Chemistry and Chemical Engineering
Yan Xiong
Jinlan Wang
Zhong Jin
State Key Laboratory of Coordination Chemistry, MOE Key Laboratory of Mesoscopic Chemistry, MOE Key Laboratory of High Performance Polymer Materials and Technology, Jiangsu Key Laboratory of Green Energy Catalysis and Intelligent Chemical Engineering, Suzhou Key Laboratory of Green Intelligent Manufacturing of New Energy Materials and Devices, Tianchang New Materials and Energy Technologies Research Center, Institute of Green Chemistry and Engineering, School of Chemistry and Chemical Engineering
Youfa Zhang
School of Materials Science and Engineering Southeast University Nanjing Jiangsu China