Electrolyte Composition-Dependent Product Selectivity in CO2 Reduction with a Porphyrinic Metal-Organic Framework Catalyst

Abstract

A copper porphyrin-derived metal-organic framework electrocatalyst, FICN-8, was synthesized and its catalytic activity for CO₂ reduction reaction (CO₂RR) was investigated. FICN-8 selectively catalyzed electrochemical reduction of CO₂ to CO in anhydrous acetonitrile electrolyte. However, formic acid became the dominant CO₂RR product with the addition of a proton source to the system. Mechanistic studies revealed the change of major reduction pathway upon proton source addition, while catalyst-bound hydride (*H) species was proposed as the key intermediate for formic acid production. This work highlights the importance of electrolyte composition on CO₂RR product selectivity.

Keywords: CO2 reduction; electrocatalysis; metalloporphyrin; metal–organic framework.