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-Cu 14 cba, Poly-Cu 6 Au 6 cbz and Poly-Cu 6 Ag 4 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-Cu 14 cba was evaluated as an electrocatalyst for reducing nitrate (NO 3 - ) to ammonia (NH 3 ), which exhibited ≈4-fold NH 3 yield rate and ≈2-fold Faraday efficiency enhancement compared to that of Cu 14 cba with good durability. Similarly, Poly-Cu 6 Au 6 cbz showed 10 times higher photocatalytic efficiency towards chemical warfare simulants degradation than the cluster counterpart.