Porphyrin-based Covalent Organic Polymers with Bimetallic Active Sites for Boosting Photocatalytic CO₂ Cycloaddition

Abstract

The photocatalytic CO₂ cycloaddition to prepare high value-added chemicals, such as cyclic carbonates (CCs) under mild conditions is an effective strategy to realize carbon neutrality. Herein, through a three-step reaction, the porphyrin-based covalent organic polymer with bimetallic active sites (Fe-COP-Zr) is successfully obtained by coordinating Fe²⁺ and Zr⁴⁺ with porphyrin and bipyridine (Bpy), respectively. Owing to excellent photosensitivity of porphyrin moieties, Fe-COP-Zr exhibits outstanding visible light absorption, which is very important for the production of photogenerated carriers. Consequently, Fe-COP-Zr shows high photocatalytic performance towards CO₂ cycloaddition with a yield of 12.1 mmol/h, which is 6 times higher than that of pure covalent organic polymer (COP) and 3 times higher than that of monometallic Fe-COP. The reason for this excellent photocatalytic CO₂ cycloaddition performance may be ascribed to the synergistic effect of Fe and Zr sites. The photogenerated electrons are easily injected into epichlorohydrin (ECH) through Fe—O bonds to form affluent electron transition state, and interact with Zr⁴⁺ as Lewis acid sites for the ring-opening of ECH, which is the rate-determining step for the visible light boosted chemical fixation of CO₂ into CCs. This work might provide some insights for design and preparation of COPs with multiple active sites to modulate their photocatalytic activities.

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