DFT comparison of the performance of bare Cu and Cu-alloyed Co single-atom catalyst for CO2 synthesizing of methanol

Copper-based catalysts have been widely used for CO 2 synthesizing of methanol, while enhancing the productivity of methanol is a big challenge. Here, we chose Co as the partner of Cu, designed an alloyed Co single-atom catalyst (SAC), and calculated its catalytic performance for the hydrogenation of CO 2 to CH 3 OH using density functional theory. Potential energy surface analysis confirmed that the favorable hydrogenation catalyst for CO 2 is the SAC of Cu 12 Co and proceeds via CO 2 → HCOO → H 2 COO → H 2 CO → H 3 CO → CH 3 OH. It has long been proposed that gas-phase atomic clusters that can be well characterized by computational method are the ultimate single-site catalysts. Brønsted–Evans–Polanyi (BEP) relations perform adequately for exploring biomass-relevant chemical kinetics on metal surface with higher accuracy than the universal BEP relations. After BEP relation analysis, the C–H formation and C–O bond scission have shown good correlation within the range considered, and for O–H, the state of initial representation seems more than adequate. We hope that our work may be useful for designing and optimizing Cu-based catalysts for CO 2 synthesizing of methanol.