Charge transfer and orbital reconstruction of non‐noble transition metal single‐atoms anchored on Ti_(2)CT_(x)‐MXenes for highly selective CO_(2) electrochemical reduction

作     者：Neng Li Jiahe Peng Zuhao Shi Peng Zhang Xin Li 李能;彭嘉禾;史祖皓;张鹏;李鑫

作者机构：State Key Laboratory of Silicate Materials for ArchitecturesWuhan University of TechnologyWuhan 430070HubeiChina Shenzhen Research Institute of Wuhan University of TechnologyShenzhen 518000GuangdongChina State Center for International Cooperation on Designer Low Carbon&Environmental Materials(CDLCEM)School of Materials Science and EngineeringZhengzhou UniversityZhengzhou 450001HenanChina Institute of Biomass EngineeringKey Laboratory of Energy Plants Resource and UtilizationMinistry of Agriculture and Rural AffairsSouth China Agricultural UniversityGuangzhou 510642GuangdongChina 

基　　金：国家自然科学基金(21975084,51672089) 湖北省自然科学基金杰出青年基金(2020CFA087) 霍英东教育基金会青年教师基金(161008) 深圳市基础研究计划(JCYJ20190809120015163) 中央政府引导地方科技发展基金自由探索基础研究(2021SVUP106) 中国创新海外专家引进项目(B18038) 中央高校基本科研基金(2022WUT) 广东省自然科学基金面上项目(2022A1515011303) 

出 版 物：《Chinese Journal of Catalysis》 (催化学报（英文）)

年 卷 期：2022年第43卷第7期

页      码：1906-1917页

摘      要：Inspired by MXene nanosheets and their regulation of surface functional groups,a series of Ti_(2)C‐based single‐atom electrocatalysts(TM@Ti_(2)CT_(x),TM=V,Cr,Mn,Fe,Co,and Ni)with two dif‐ferent functional groups(T=–O and–S)was *** CO_(2)RR catalytic performance was stud‐ied using well‐defined ab initio *** results show that the CO_(2) molecule can be more readily activated on TM@Ti_(2)CO_(2) than the TM@Ti_(2)CS_(2) *** charge analysis reveals that the Ti_(2)CO_(2) substrate is involved in the adsorption reaction,and enough electrons are injected into the 2π*u orbital of CO_(2),leading to a V‐shaped CO_(2) molecular configuration and partial negative charge *** V‐shaped CO_(2) further reduces the difficulty of the first hydrogenation reac‐tion *** calculatedΔG of the first hydrogenation reaction on TM@Ti_(2)CO_(2) was significantly lower than that of the TM@Ti_(2)CS_(2) ***,the subsequent CO_(2) reduction pathways show that the UL of the potential determining step on TM@Ti_(2)CS_(2) is smaller than that of TM@Ti_(2)CO_(2).Combining the advantages of both TM@Ti_(2)CS_(2) and TM@Ti_(2)CO_(2),we designed a mixed functional group surface with–O and–S to anchor TM *** results show that Cr atoms an‐chored on the surface of mixed functional groups exhibit high catalytic activity for the selective production of *** study opens an exciting new avenue for the rational design of highly selec‐tive MXene‐based single‐atom CO_(2)RR electrocatalysts.

主 题 词：TM@Ti_(2)CTx MXene Single‐atom catalyst CO_(2)RR Orbital reconstruction Charge transform Mixed functional group surface 

学科分类：081705[081705] 08[工学] 0817[工学-轻工类] 

核心收录：

D　O　I：10.1016/S1872-2067(21)64018-4

馆 藏 号：203111743...