Electrocatalytic Syngas Production Using Metalloporphyrins with Controllable H2/CO Ratios

Abstract Electrochemical methods to produce syngas present a promising strategy for energy conservation and environmental protection. The H₂/CO ratio of syngas is crucial for its applications. However, few catalysts can achieve catalytic generation of syngas that can be directly used because the H₂/CO ratio is difficult to be controlled. To address this issue, bicomponent electrocatalysts are utilized to produce syngas with controllable H₂/CO ratios. These two catalysts in the bicomponent electrocatalysts can efficiently and selectively catalyze CO 2 reduction reaction (CO 2 RR) to generate CO and hydrogen evolution reaction (HER) to generate H 2 respectively. Metalloporphyrins are promising electrocatalysts for both CO 2 RR and HER. A series of metalloporphyrins 1‐M ( M = Fe , Co , Ni , Cu ) were synthesized as electrocatalysts to produce syngas with different H 2 /CO ratios. Among these metalloporphyrins, 1‐Co and 1‐Cu can selectively produce CO and H 2 , respectively, through CO 2 RR and HER in KHCO 3 aqueous solutions. The ratio of 1‐Co and 1‐Cu in bicomponent electrocatalysts 1‐Co / 1‐Cu is adjusted to achieve the regulation of H 2 /CO ratio (0.1–6.4) at high catalytic currents. This work provides a new approach for designing more efficient syngas catalysts with tunable H 2 /CO ratios.