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

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.