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 (Y-3(C6X6)(2)), where Y indicates Co, Cu, Pd, Pt; and X indicates organic ligands; (NH, NHS, 5) for CO2 RR. The 2D Y-3(C6X6)(2) monolayers unveiled metallic behavior due to the suitable pi electron conjugation network and the productive interaction among the metal atom, organic ligands, and benzene rings, except for Co-3(C6S6)(2), which revealed semiconducting behavior. Significantly, the catalytic performance of Y-3(C6X6)(2) is influenced by the strength of interaction between the CO2 RR intermediates and the metal complex (Y-X-4), which may be altered by varying the central metal atom with different d-electron orbitals or by organic ligands. Surprisingly, Co-3(C-6(NH)(3)S-3)(2), Co-3(C-6(NH)(3))(2), and Cu-3(C6S6)(2) have excellent CO2RR to formic acid activity. Whereas, Pt-3(C-6(NH)(3))(2) and Pc-3(C-6(NH)(3))(2) shows good CO2RR to carbon mono-oxide activity. Our research provides imperative insights for designing and screening efficient CO2 RR 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.

Automated summary

This study explores the electrocatalytic performance of two-dimensional metal-organic frameworks in CO2RR using density functional theory, and finds that the catalytic performance can be altered by changing the metal atom or organic ligands. The research provides important insights for designing and screening efficient CO2RR catalysts, and suggests the development of metal-organic frameworks with beneficial properties.