Electropolymerization of Metal Clusters Establishing a Versatile Platform for Enhanced Catalysis Performance

Atomically precise metal clusters are attractive as highly efficient catalysts, but suffer from continuous efficiency deactivation in the catalytic process. Here, we report the development of an efficient strategy that enhances catalytic performance by electropolymerization (EP) of metal clusters into hybrid materials. Based on carbazole ligand protection, three polymerized metal-cluster hybrid materials, namely Poly-Cu₁₄cba, Poly-Cu₆Au₆cbz and Poly-Cu₆Ag₄cbz, were prepared. Compared with isolated metal clusters, metal clusters immobilizing on a biscarbazole network after EP significantly improved their electron-transfer ability and long-term recyclability, resulting in higher catalytic performance. As a proof-of-concept, Poly-Cu₁₄cba was evaluated as an electrocatalyst for reducing nitrate (NO₃⁻) to ammonia (NH₃), which exhibited ≈4-fold NH₃ yield rate and ≈2-fold Faraday efficiency enhancement compared to that of Cu₁₄cba with good durability. Similarly, Poly-Cu₆Au₆cbz showed 10 times higher photocatalytic efficiency towards chemical warfare simulants degradation than the cluster counterpart.