第一性原理研究单原子氮碳催化剂电催化还原二氧化碳

First-principles study on single-atom nitrogen-carbon catalysts for electrocatalytic reduction of carbon dioxide

为了显著提升CO_(2)还原反应(CO_(2)RR)中催化剂的性能,本文利用第一性原理计算方法,建立单层氮掺杂石墨烯负载的过渡金属单原子催化剂(TM-C_(2)N,TM=Cu、Pd、Ag、Fe、Ni、Sn),用于CO_(2)还原为CO和HCOOH。计算结果表明,TM-C_(2)N催化剂具有高结构稳定性、高效吸附和活化CO_(2)能力,以及良好的抑制析氢反应(HER)性能。吉布斯自由能计算结果表明,CO_(2)RR在TM-C_(2)N上以不同的反应路径生成HCOOH和CO。极限电位证明,Fe-C_(2)N和Cu-C_(2)N催化性能最好。这些计算结果不仅为C_(2)N基催化剂的实验调控提供了理论依据,而且对开发其他过渡金属高效电催化剂CO_(2)RR具有指导意义。

To significantly improve the performance of catalysts for the CO_(2)reduction reaction(CO_(2)RR),TM single-atom catalysts supported on nitrogen-doped graphene monolayers(TM-C_(2)N,TM=Cu,Pd,Ag,Fe,Ni,Sn)were designed for the conversion of CO_(2)to CO and HCOOH using first-principles calculations.The results indicated that the TM-C_(2)N catalysts exhibit high structural stability,efficient CO_(2)adsorption and activation,and strong suppression of the hydrogen evolution reaction(HER).Based on Gibbs free energy calculations,CO_(2)RR proceeds on TM-C_(2)N through different pathways to generate HCOOH and CO.The limiting potential calculations revealed that Fe-C_(2)N and Cu-C_(2)N catalysts exhibit the highest catalytic activity.These findings not only provide a theoretical basis for the experimental modulation of C_(2)N-based catalysts but also offer valuable insights for the development of other efficient transition metal electrocatalysts for CO_(2)RR.