Electrocatalytic CO2 Reduction Activity Over Transition Metal Anchored on Nitrogen-Doped Carbon: A Density Functional Theory Investigation

The electrochemical CO2 reduction reaction (ERCO2) is a promising technology for converting waste CO2 into chemicals which could be used as feedstock for the chemical industry or as synthetic fuels. The development of catalysts for the electrochemical reduction of carbon dioxide (ERCO2) with high activity and selectivity remains a grand challenge to render the technology useably. In this work, we studied the electrocatalysis CO2 reduction process of metal-nitrogen-carbon (M-NC) catalysts using metal atoms as the active center (M-NC, M = Fe, Os and Ru) as a model, and performing density functional (DFT) calculations. The calculation shows that the limiting potential required for methane formation over Fe-NC catalyst is the minimum (* + CO2+ 8H(+) -> C*OOH + 7H(+) -> C*O + 6H(+) -> *CHO + 5H(+) -> CH2O* + 4H(+) -> CH3O* + 3H(+) -> CH3O*H + 2H(+)-> *CH3 + H+ -> * + CH4). At the same time, we use the d-band center theory to study the accuracy of the reaction steps. The d-band center value of Fe-NC is closer to E-F than Os-NC and Ru-NC. This in-depth understanding of ERCO2 activity and selectivity based on metal morphology in NC provides guidance for the rational design of ERCO2 by M-NC catalysts for its application in high-performance equipment. [GRAPHICS] .