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 CO₂ 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 Cu² ⁺ ions. Systematic evaluation reveals that the bimetallic Cu@Azo-CoPG outperforms its monometallic counterparts (Cu-PG and Co-PG) in CO₂ reduction reaction (CO₂RR), 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 CO₂ adsorption/activation and product desorption kinetics, offering new insights into the rational engineering of dual-active-site catalysts for sustainable energy conversion.