Conductive Covalent Organic Frameworks of Polymetallophthalocyanines as a Tunable Platform for Electrocatalysis
Yi Zhang, Xiyuan Zhang, Long Jiao, Zheng Meng, Hai‐Long Jiang
Abstract
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 ( p MPcs, 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 p MPcs a unique platform in electrochemical catalysis, where tunability emerges from long-range interactions. The construction of p CoNiPc with a Co and Ni dual-site integrates the advantageous features of p CoPc and p NiPc in electrocatalytic CO 2 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, FE CO = 94%), and stability (>10 h), making it one of the best-performing reticular materials.