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-Cu₁₄ cba, Poly-Cu₆ Au₆ cbz and Poly-Cu₆ Ag₄ cbz, 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-Cu₁₄ cba 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 Cu₁₄ cba with good durability. Similarly, Poly-Cu₆ Au₆ cbz showed 10 times higher photocatalytic efficiency towards chemical warfare simulants degradation than the cluster counterpart.