Local Weak Hydrogen Bonds Significantly Enhance CO2 Electroreduction Performances of a Metal-Organic Framework

扫码查看

原文链接

NETL
NSTL
万方数据

外文摘要：Technological application of the electrochemical reduction of CO2 relies on efficient electrocatalysts.We demonstrate that the introduction of amino groups alongside the porphyrin cobalt centers in a metal-organic framework(MOF)can dramatically accelerate the electrochemical CO2 reduction performance.A classic cobalt porphyrin-based MOF showing moderate C02-to-CO electroreduction performance(turnover frequency[TOF]=0.20 s-1,Faradic efficiency[FE]=47.4％)is modified.By mo-lecular design of the porphyrin-based ligand,amino groups are introduced alongside the cobalt center,giving remarkably enhanced Co2-to-CO electro-reduction performance as high as FE 99.4％,current density 7.2 mA cm-2,and TOF 21.17 s-1,in a near-neutral aqueous solution at a low overpotential of 525 mV.Density functional theory calculations showed that the prepositioned amino groups,al-though located not sufficiently close to the active center,serve as hydrogen-bonding donors to stabilize the intermediate Co-CO2 adduct and impede the for-mation of Co-H2O adduct,which not only promotes the CO2 reduction reaction but also restrains the hydrogen evolution reaction.

外文关键词：

CO2 electroreductionmetal-organic frameworkshydrogen bondporphyrinamino groups

作者：

Yu Wang、Ning-Yu Huang、Hao-Yu Wang、Xue-Wen Zhang、Jia-Run Huang、Pei-Qin Liao、Xiao-Ming Chen、Jie-Peng Zhang

展开 >

作者单位：

MOE Key Laboratory of Bioinorganic and Synthetic Chemistry,School of Chemistry,Sun Yat-Sen University,Guangz-hou 510275

基金：

国家重点研发计划国家自然科学基金国家自然科学基金国家自然科学基金国家自然科学基金国家自然科学基金Guangdong Pearl River Talents Program广东省自然科学基金杰出青年基金

项目编号：

2021YFA150040121890380218210032207127221975290217310072017BT01C1612018B030306009

出版年：

2023

DOI：

10.31635/ccschem.022.202202062

中国化学会会刊(英文)

CSCD

ISSN：

年,卷(期)：2023.5(1)

参考文献量61