Phthalocyanine‐Based Bimetallic Azo Polymers as Highly Efficient Electrocatalysts for CO ₂ Reduction to CO

ABSTRACT Tailoring bimetallic synergy in azo‐functionalized porous organic polymers for enhanced electrocatalytic CO ₂ reduction porous organic polymers (POPs) have emerged as promising candidates for electrocatalytic applications due to their structural tunability and high surface areas. In this study, we report a coordination‐driven assembly strategy to construct a Cu/Co bimetallic azo‐phenolic polymer (denoted as Cu@Azo‐CoPG) through chelation of azo‐phenolic motifs with Cu ^{2 +} ions. Systematic evaluation reveals that the bimetallic Cu@Azo‐CoPG outperforms its monometallic counterparts (Cu‐PG and Co‐PG) in CO ₂ reduction reaction (CO ₂ RR), achieving a remarkable CO Faraday efficiency (FE _CO ) of 94.3%. First‐principles calculations elucidate that the Cu─Co dual sites synergistically modulate reaction energetics: the Co center lowers the energy barrier for ^* COOH intermediate formation, while adjacent Cu sites facilitate CO desorption. This work establishes a design paradigm where the electronic interplay between heterometallic sites in POPs enhances both CO ₂ adsorption/activation and product desorption kinetics, offering new insights into the rational engineering of dual‐active‐site catalysts for sustainable energy conversion.