CO2 electrochemical reduction boosted by the regulated electronic properties of metalloporphyrins through tuning an atomic environment

Abstract

The large amount of carbon dioxide (CO₂) emissions has seriously threatened the living environment of human beings. Electrocatalytic conversion of CO₂ is one of the most promising methods as it can not only reduce the hazards associated with excessive emissions but also obtain fuels or other chemicals. Current research has found that the changes in the performance of catalysts are caused by the external environment, but their mechanisms affecting CO₂ reduction are still not clear enough. Herein, based on density functional theory (DFT) calculations, ions X (X = Cl⁻, Na⁺ and S²⁻) were introduced to change the atomic environment of metalloporphyrins (MPPs). The effects of the atomic environment of the active site on CO₂ catalytic performance were systematically investigated. Our results show that the doping of ions regulates the metal electronic state, which can change the CO₂ catalytic activity and selectivity on MPPs. Deeply understanding the CO₂ reduction mechanism provides a theoretical fundament for designing high-performance and high-selectivity CO₂ electrochemical reduction schemes.