Microstructure Design Strategy for Molecularly Dispersed Cobalt Phthalocyanine and Efficient Mass Transport in CO₂ Electroreduction

Abstract Cobalt phthalocyanine (CoPc) has attracted particular interest owing to its excellent activity during the electrochemical CO₂ conversion to CO. However, the efficient utilization of CoPc at industrially relevant current densities is still a challenge owing to its nonconductive property, agglomeration, and unfavorable conductive substrate design. Here, a microstructure design strategy for dispersing CoPc molecules on a carbon substrate for efficient CO₂ transport during CO₂ electrolysis is proposed and demonstrated. The highly dispersed CoPc is loaded on a macroporous hollow nanocarbon sheet to act as the catalyst (CoPc/CS). The unique interconnected and macroporous structure of the carbon sheet forms a large specific surface area to anchor CoPc with high dispersion and simultaneously boosts the mass transport of reactants in the catalyst layer, significantly improving the electrochemical performance. By employing a zero‐gap flow cell, the designed catalyst can mediate CO₂ to CO with a high full‐cell energy efficiency of 57% at 200 mA cm⁻².