Weak Bimetal Coupling-Assisted MN Catalyst for Enhanced Carbon Dioxide Reduction Reaction.

The design of multimetal catalysts holds immense significance for efficient CO capture and its conversion into economically valuable chemicals. Herein, heterobimetallic catalysts (MM)L were exploited for the CO reduction reactions (CORR) using relativistic density functional theory (DFT). The octadentate Pacman-like polypyrrolic ligand (HL) accommodates two metal ions (Mo, W, Nd, and U) inside (M) and outside (M) its month, rendering a weak bimetal coupling-assisted MN catalytically active site. Adsorption reactions have access to energetically stable coordination modes of -CO, -C, and -(CO), where the donor atom(s) are marked in bold. Among all of the species, (UMo)L releases the most energy. Along CORR, it favors to produce CO. The high-efficiency CO reduction is attributed to the size matching of U with the ligand mouth and the effective manipulation of the electron density of both ligand and bimetals. The mechanism in which heterobimetals synergetically capture and reduce CO has been postulated. This establishes a reference in elaborating on the complicated heterogeneous catalysis.