Benchmarking the two-dimensional conductive Y3(C6X6)2 (Y = Co, Cu, Pd, Pt; X = NH, NHS, S) metal-organic framework nanosheets for CO2 reduction reaction with tunable performance

Scrutinizing competent and economical electrocatalysts for carbon-di-oxide reduction reactions (CO2RR) is essential for wide-range commercialization of livestock feed. Therefore, via density functional theory (DFT), we broadly explored the electrocatalytic performance of two-dimensional (2D) metal−organic frameworks (Y3(C6X6)2), where Y indicates Co, Cu, Pd, Pt; and X indicates organic ligands; (NH, NHS, S) for CO2RR. The 2D Y3(C6X6)2 monolayers unveiled metallic behavior due to the suitable π electron conjugation network and the productive interaction among the metal atom, organic ligands, and benzene rings, except for Co3(C6S6)2, which revealed semiconducting behavior. Significantly, the catalytic performance of Y3(C6X6)2 is influenced by the strength of interaction between the CO2RR intermediates and the metal complex (Y-X4), which may be altered by varying the central metal atom with different d-electron orbitals or by organic ligands. Surprisingly, Co3(C6(NH)3S3)2, Co3(C6(NH)3)2, and Cu3(C6S6)2 have excellent CO2RR to formic acid activity. Whereas, Pt3(C6(NH)3)2 and Pd3(C6(NH)3)2 shows good CO2RR to carbon mono-oxide activity. Our research provides imperative insights for designing and screening efficient CO2RR catalysts. This research put forward the idea of developing metal-organic frameworks with beneficial properties to meet the specific requirements of diverse research areas, such as catalysis, energy storage, and molecular sensing.