The development of low-cost,high-performance 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 function...The development of low-cost,high-performance 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 alloy 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 demonstrate that catalytic performance is predominantly determined 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 CO_(2)at C-sites catalyzes the reduction of CO_(2)to CH_(4).This theoretical research provides valuable insights into the fundamental processes and energy landscapes involved in converting CO_(2)to CH_(4)on the studied catalytic structure,potentially paving the way for more efficient and sustainable carbon dioxide utilization strategies.展开更多
基金the National Natural Science Foundation of China(22203046 and 52102265)Jiangsu Provincial Natural Science Foundation(BK20230368 and BK20210604)+2 种基金the Project of State Key Laboratory of Organic Electronics and Information Displays,Nanjing University of Posts and Telecommunications(GZR2023010003,GZR2022010017 and GDX2022010010)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications(NY221128,NY223099 and NY223054)the Natural Science Research Start-up Foundation of Recruiting Talents of Suzhou Vocational Institute of Industrial Technology(SYG202354)。
文摘The development of low-cost,high-performance 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 alloy 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 demonstrate that catalytic performance is predominantly determined 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 CO_(2)at C-sites catalyzes the reduction of CO_(2)to CH_(4).This theoretical research provides valuable insights into the fundamental processes and energy landscapes involved in converting CO_(2)to CH_(4)on the studied catalytic structure,potentially paving the way for more efficient and sustainable carbon dioxide utilization strategies.
