Tip-structure coupled with hydrophobic effect synergistically regulate microenvironment for efficient CO2 electroreduction in acidic electrolytes

作     者：Dong, Tian Wang, Weizhou Yang, Qin Geng, Yanling Du, Yunmei Liu, Kang Wu, Zexing Lai, Jianping Li, Bin Zheng, Gengfeng Li, Hongdong Wang, Lei 

作者机构：Key Laboratory of Eco-Chemical Engineering International Science and Technology Cooperation Base of Eco-Chemical Engineering and Green Manufacturing Qingdao University of Science and Technology Qingdao266042 China College of Chemistry and Molecular Engineering Qingdao University of Science and Technology Qingdao266042 China Laboratory of Advanced Materials Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Faculty of Chemistry and Materials Science Fudan University Shanghai200438 China 

出 版 物：《Applied Catalysis B: Environmental》 (Appl. Catal. B Environ.)

年 卷 期：2025年第375卷

核心收录：

学科分类：0819[工学-矿业工程] 0808[工学-电气工程] 081704[工学-应用化学] 0809[工学-电子科学与技术（可授工学、理学学位）] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 070203[理学-原子与分子物理] 070207[理学-光学] 0806[工学-冶金工程] 0817[工学-化学工程与技术] 0703[理学-化学] 0803[工学-光学工程] 0702[理学-物理学] 

基　　金：This work was supported by the National Natural Science Foundation of China (22302108  52072197  52272222  and U23A20552)  Taishan Scholar Young Talent Program (tsqn201909114)  Youth Innovation and Technology Foundation of Shandong Higher Education Institutions  China (2023KJ313)  Natural Science Foundation of Qingdao (23\u20132\u20131\u201312-zyyd-jch)  Qingdao Postdoctoral Researcher Applied Research Project (QDBSH20220202043) 

主　　题：Electrolytic reduction 

摘      要：In acidic CO2 electro-reduction, the strong hydrogen evolution reaction (HER) and the catalyst s susceptibility to corrosion limit its selectivity, stability and energy efficiency. We demonstrate that the enhanced the activity and stability of CO2 reduction reaction (CO2RR) with suppressed HER can be achieved by synergistically modulating the local microenvironment using tip-enhanced electric field effect and hydrophobic effect. This enabled a Faraday efficiency (FE) of 93.2 % and a cathode energy efficiency of 49.36 % for CO at the current density up to −400 mA cm−2 over 32 h on polytetrafluoroethylene (PTFE) modified silver nanoneedles catalyst (Ag-NNs@PTFE) in a flow cell with pH = 2. Finite element modelling and density functional theory revealed that silver nanoneedles catalyst could induce high local potassium ion (K+) concentration to stabilize key intermediates of CO2RR, and PTFE-modified catalyst inter faces generated energetically favorable pathways for CO2RR. Furthermore, the coated PTFE could protect catalyst against corrosion. Meanwhile, this strategy has also been well applied on bismuth-based catalyst with nanoneedle structures. The optimal Bi-NNs@PTFE exhibited the FE of HCOOH maintaining above 85 % over 32 h of operation at −1.1 V vs. RHE. This work provides a new idea for the application of CO2RR in acidic media. © 2025 Elsevier B.V.