Single‐Atom Molybdenum‐N3 Sites for Selective Hydrogenation of CO2 to CO

Abstract

AbstractThe design of efficient non‐noble metal catalysts for CO2 hydrogenation to fuels and chemicals is desired yet remains a challenge. Herein, we report that single Mo atoms with a MoN3 (pyrrolic) moiety enable remarkable CO2 adsorption and hydrogenation to CO, as predicted by density functional theory studies and evidenced by a high and stable conversion of CO2 reaching about 30.4 % with a CO selectivity of almost 100 % at 500 °C and very low H2 partial pressure. Atomically dispersed MoN3 is calculated to facilitate CO2 activation and reduces CO2 to CO* via the direct dissociation path. Furthermore, the highest transition state energy in CO formation is 0.82 eV, which is substantially lower than that of CH4 formation (2.16 eV) and accounts for the dominant yield of CO. The enhanced catalytic performances of Mo/NC originate from facile CO desorption with the help of dispersed Mo on nitrogen‐doped carbon (Mo/NC), and in the absence of Mo nanoparticles. The resulting catalyst preserves good stability without degradation of CO2 conversion rate even after 68 hours of continuous reaction. This finding provides a promising route for the construction of highly active, selective, and robust single‐atom non‐precious metal catalysts for reverse water–gas shift reaction.