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

This is the authors' abstract. We don't add key points for this paper.

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.