铜基团簇上原子级精确的局部环境调控促进CO2到CH4的电催化还原
Electrocatalytic conversion of CO2 to CH4 over Cu-based cluster via atomically precise local environment modulation
史丽 1吴涵博 1徐文迪 1付伟 1王晓冰 1顾郑煜 1张秀云 2陈剑宇 1马延文 3赵进1
作者信息
- 1. State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials(IAM),Nanjing University of Posts and Telecommunications,Nanjing 210023,China
- 2. College of Physics Science and Technology,Yangzhou University,Yangzhou 225002,China
- 3. State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials(IAM),Nanjing University of Posts and Telecommunications,Nanjing 210023,China;Suzhou Vocational Institute of Industrial Technology,Suzhou International Education Park,Suzhou 215104,China
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摘要
在原子尺度上开发低成本、高性能催化剂已成为可再生清洁能源技术大规模应用的一个关键问题.本文中基于密度泛函理论计算,我们系统研究了过渡金属(Fe、Co和Ni)局部掺杂Cu13/55团簇形成的单/多原子合金对电化学CO2还原反应活性和选择性的影响.研究发现多原子合金团簇的催化性能远超Cu(211)表面,尤其是Co666构型表现出卓越的性能,速决步自由能垒仅为0.33 eV.此外,我们的研究显示合金团簇的催化性能主要由配位数为6(CN=6)的掺杂金属比例决定.这一比例主要影响关键中间体(HCOO*和H2COO*)的吸附强度.结合Bader电荷分析和自由能计算,我们提出了新的CO2还原机理,即吸附的CO2的C位点不断被氢化并最终还原为CH4.这项研究为团簇结构催化CO2转化为CH4提供了理论基础.
Abstract
The development of low-cost,high-perfor-mance catalysts at the atomic scale has become a challenging issue for the large-scale applications of renewable clean energy technologies.Herein,on the basis of density functional theory calculation,we systematically investigate the effect of the local environment on the activity and selectivity of electrochemical carbon dioxide reduction reaction over single/multi-atom al-loy clusters formed by the transition metal(Fe,Co,and Ni)-doped Cu13/55 clusters.Our findings reveal that the catalytic performance of multi-atom alloy clusters far exceeds that of Cu(211)surface.Notably,the Co666 configuration exhibits exceptional performance with a remarkably low free energy barrier of just 0.33 eV.Furthermore,our investigations de-monstrate that catalytic performance is predominantly de-termined by the relative proportion of modifying metallic dopant species that generate a coordination number of 6.This ratio principally influences the adsorption strength of key intermediates(HCOO*and H2COO*).Bader charge analyses and free energy calculations elucidate a new mechanistic pathway,wherein the hydrogenation of CO2 at C-sites cata-lyzes the reduction of CO2 to CH4.This theoretical research provides valuable insights into the fundamental processes and energy landscapes involved in converting CO2 to CH4 on the studied catalytic structure,potentially paving the way for more efficient and sustainable carbon dioxide utilization strategies.
关键词
electrocatalytic CO2 reduction/nanocluster/catalyst modulation/first-principles calculationsKey words
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出版年
2024
NETL
NSTL
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