Tuning the local coordination environment of silver(Ⅰ) coordination networks with counterions for enhanced electrocatalytic CO_(2) reduction  

作　　者：Xiaofeng Cui Xueting Wang Cong Fu Bing Liu Mei-Yan Gao Tingting Kong Yujie Xiong 

机构地区：[1]Anhui Engineering Research Center of Carbon Neutrality,The Key Laboratory of Functional Molecular Solids,Ministry of Education,Anhui Laboratory of Molecular-Based Materials,College of Chemistry and Materials Science,Anhui Normal University,Wuhu 241002,China [2]Department of Chemical Sciences,Bernal Institute,University of Limerick,Limerick V94 T9PX,Republic of Ireland [3]School of Chemistry and Materials Science,University of Science and Technology of China,Hefei 230026,China [4]School of Chemical and Material Engineering,Jiangnan University,Wuxi 214122,China

出　　处：《Science China Chemistry》2024年第5期1524-1530,共7页中国科学（化学英文版）

基　　金：supported by financial support in part by NSFC (91961106, 51902253, 21725102);Anhui Provincial Natural Science Foundation (Grant 2108085MB46);Key Project of Youth Elite Support Plan in Universities of Anhui Province (Grant gxyqZD2021121);Shaanxi Provincial Natural Science Foundation (2020JQ-778)。

摘　　要：Very recently, the local coordination environment of active sites has been found to strongly influence their performance in electrocatalytic CO_(2) reduction by tuning the intrinsic kinetics of CO_(2) activation and intermediate stabilization. It is imperative to elucidate the mechanism for such an influence towards the rational design of efficient catalysts;however, the complex interactions between the multiple factors involved in the system make it challenging to establish a clear structure–performance relationship. In this work, we chose ion-intercalated silver(I)-based coordination networks(AgCNs) with a well-defined structure as a model platform, which enables us to understand the regulation mechanism of counterions as the counterions are the only tuning factor involved in such a system. We prepared two isostructural Ag CNs with different intercalation ions or counterions of BF_(4)^(-) and ClO_(4)^(-)(named as AgCNs-BF_(4) and AgCNs-ClO_(4)) and found that the former has a more competitive CO_(2) electroreduction performance than the latter. AgCNs-BF_(4) achieves the highest Faradaic efficiency for CO_(2) to CO of 87.1% at-1.0 V(vs. RHE) with a higher partial current density, while AgCNs-ClO_(4) exhibits only 77.2% at the same applied potential.Spectroscopic characterizations and theoretical calculation reveal that the presence of BF_(4)^(-)is more favorable for stabilizing the COOH^(*) intermediate by weakening hydrogen bonds, which accounts for the superior activity of Ag CNs-BF_(4).

关 键 词：electrocatalytic CO_(2) reduction coordination networks local environment COUNTERIONS intercalation ions 

分 类 号：O643.36[理学—物理化学]