TM and P dual sites on polymeric carbon nitride enable highly selective CO reduction to C2 products with low potentials: A theoretical perspective

The CO reduction reaction (CORR) for the production of high-value-added multi-carbon (C2+) products is currently being actively investigated, where searching for high-efficiency catalysts with moderate CO intermediate binding strength and low kinetic barrier for C–C coupling poses a significant challenge. In this study, we employed density functional theory computations to design four synergistic coupling dual sites catalysts for CORR to C2 products, namely, TM-P@melon, by co-doping transition metals (TM = Mn, Fe, Co, and Ni) and phosphorus (P) into the polymeric carbon nitride (i.e., melon-CN). Mn–P@melon and Ni–P@melon exhibit higher selectivity toward C2H5OH and C2H6, respectively, with limiting potentials (C–C coupling kinetic energy barriers) of −0.43 V (0.52 eV) and −0.17 V (0.26 eV), respectively. The introduction of TM and P atoms not only narrows the band gap of melon-CN but also favors the coupling of CO and *CHO, providing an active site for C–C coupling, thus facilitating the catalytic reaction. Our work provides rational insights for the design of stable, low-cost, and efficient CORR dual sites catalysts that facilitate the sustainable production of high-value C2 chemicals and fuels.