Conductive Covalent Organic Frameworks of Polymetallophthalocyanines as a Tunable Platform for Electrocatalysis

Developing an electrocatalyst platform that can control the interplay among activity, selectivity, and stability at atomic precision remains a grand challenge. Here, we have synthesized highly crystalline polymetallo­phthalocyanines (pMPcs, M = Fe, Co, Ni, and Cu) through the annulation of tetracyanobenzene in the presence of transition metals. The conjugated, conductive, and stable backbones with precisely installed metal sites render pMPcs a unique platform in electrochemical catalysis, where tunability emerges from long-range interactions. The construction of pCoNiPc with a Co and Ni dual-site integrates the advantageous features of pCoPc and pNiPc in electrocatalytic CO2 reduction through electronic communication of the dual-site with an unprecedented long atomic separation of ≥14 chemical bonds. This integration provides excellent activity (current density, j = −16.0 and −100 mA cm–2 in H-type and flow cell, respectively), selectivity (CO Faraday efficiency, FECO = 94%), and stability (>10 h), making it one of the best-performing reticular materials.