Lewis-base ligand-reshaped interfacial hydrogen-bond network boosts CO_(2) electrolysis  

作　　者：Wangxin Ge Haolan Tao Lei Dong Yu Fan Yanpu Niu Yihua Zhu Cheng Lian Honglai Liu Hongliang Jiang Chunzhong Li 

机构地区：[1]Key Laboratory for Ultrafine Materials of Ministry of Education,School of Chemical Engineering,East China University of Scienceand Technology,Shanghai 200237,China [2]Shanghai Engineering Research Center of Hierarchical Nanomaterials,School of Materials Scienceand Engineering,East China University of Scienceand Technology,Shanghai 200237,China [3]State Key Laboratory of Chemical Engineering,Shanghai Engineering Research Center of Hierarchical Nanomaterials,School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237,China [4]Department of Chemical Engineering,School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China

出　　处：《National Science Review》2024年第8期258-268,共11页国家科学评论（英文版）

基　　金：supported by the National Key Research and Development Program (2022YFB3808400);the National Natural Science Foundation of China (22222804 and U22B20143);the Science and Technology Commission of Shanghai Municipality (22dz1205900);the Shanghai Municipal Science and Technology Major Project.

摘　　要：Both the catalyst and electrolyte strongly impact the performance of CO_(2) electrolysis.Despite substantial progress in catalysts,it remains highly challenging to tailor electrolyte compositions and understand their functions at the catalyst interface.Here,we report that the ethylenediaminetetraacetic acid(EDTA)and its analogs,featuring strong Lewis acid-base interaction with metal cations,are selected as electrolyte additives to reshape the catalyst-electrolyte interface for promoting CO_(2) electrolysis.Mechanistic studies reveal that EDTA molecules are dynamically assembled toward interface regions in response to bias potential due to strong Lewis acid-base interaction of EDTA^(4-)-K^(+).As a result,the original hydrogen-bond network among interfacial H2O is disrupted,and a hydrogen-bond gap layer at the electrified interface is established.The EDTA-reshaped K^(+)solvation structure promotes the protonation of^(*)CO_(2) to^(*)COOH and suppressing^(*)H_(2)O dissociation to^(*)H,thereby boosting the co-electrolysis of CO_(2) and H_(2)O toward carbon-based products.In particular,when S mM of EDTA is added into the electrolytes,the Faradaic eficiency of CO on the commercial Ag nanoparticle catalyst is increased from 57.0%to 90.0%at an industry-relevant current density of 500 mA cm^(-2).More importantly,the Lewis-base ligand-reshaped interface allows a range of catalysts(Ag,Zn,Pd,Bi,Sn,and Cu)to deliver substantially increased selectivity of carbon-based products in both H-type and flow-type electrolysis cells.

关 键 词：CO_(2)electrolysis electrode-electrolyte interface Lewis acid-base interaction hydrogen-bonding interaction AIMD simulation 

分 类 号：O646[理学—物理化学]