Regulate the adsorption of oxygen-containing intermediates to promote the reduction of CO2 2 to CH4 4 on Ni-based catalysts

The introduction of oxophilic metals can enhance the selectivity of CO2 2 reduction reactions (CO2RR) 2 RR) by modulating the adsorption of oxygen-associated active substances on the catalyst surface. Alloying lanthanide atoms into metals has been shown to improve CH4 4 selectivity by breaking the linear relationship between the adsorption energies of CO* and HxCO*. x CO*. In this work, a series of oxophilic transition metals (Fe, Mo, Co, Mn) are introduced to explore the influence on the CO2RR. 2 RR. DFT results demonstrate that the doping of oxophilic metals regulates the adsorption strength between the catalyst surface and intermediates, thereby affecting the CH4 4 and H3COH 3 COH pathways. Notably, COOH* formation is enhanced on Ni surfaces, leading to increased H3COH 3 COH production. Ni-Fe and Ni-Mo exhibit significant H3CO* 3 CO* and CO2* 2 * binding energies, which reduces the barrier for H3CO*. 3 CO*. Meanwhile, the bond energy of M-O is higher than that of C-O in H3CO*, 3 CO*, promoting the generation of CH4. 4 . The addition of Co and Mn makes the desorbed of HCOOH smaller than the hydrogenation energy barrier, which accelerates the synthesis of formic acid. This research provides a new pathway for the development of inexpensive and resource-rich catalysts.