Tuning the product selectivity of single-atom catalysts for CO₂ reduction beyond CO formation by orbital engineering

Electrochemical CO₂ reduction (CO₂R) is one of the promising strategies for developing sustainable energy resources. Single-atom catalysts (SACs) have emerged as efficient catalysts for CO₂R. However, the efficiency of SACs for the formation of reduction products beyond two-step CO formation is low due to the lower binding strength of the CO intermediate. In this study, we present an orbital engineering strategy based on density functional theory calculations and the fragment molecular orbital approach to tune product selectivity for the CO₂R reaction on macrocycle based molecular catalysts (porphyrin and phthalocyanine) and extended SACs (graphene and covalent organic frameworks) with Fe, Co, and Ni dopants. The introduction of neutral axial ligands such as imidazole, pyridine, and trimethyl phosphine to the metal dopants enhances the binding affinity of the CO intermediate. The stability of the catalysts is investigated through the thermodynamic binding energy of the axial ligands and ab initio molecular dynamics simulations (AIMD). The grand canonical potential method is used to determine the reaction free energy values. Using a unified activity volcano plot based on the reaction free energy values, we investigated the catalytic activity and product selectivity at an applied potential of -0.8 V vs. SHE and a pH of 6.8. We found that with the imidazole and pyridine axial ligands, the selectivity of Fe-doped SACs towards the formation of the methanol product is improved. The activity volcano plot for these SACs shows a similar activity to that of the Cu (211) surface. The catalytic activity is found to be directly proportional to the sigma-donating ability of the axial ligands.