Atomic Bridging of Metal‐Nitrogen‐Carbon toward Efficient Integrated Electrocatalysis

Abstract The rational design of robust electrocatalysts for efficient integrated devices is crucial to enhance energy conversion performance. The coordination of organic ligands with metal ions provides high flexibility to anchor metal atoms among carbon materials. Herein, the atomic anchoring of Zn and Ni atoms into N‐doped carbon networks with adjustable atomic structure is developed by the facile pyrolysis of metal‐organic framework nanoplates in the presence of dicyandiamide. Theoretical calculations reveal the descriptor‐based design principles to adjust the bridging structures of metal‐nitrogen‐carbon moieties with changing d‐band centers, thereby improving electrocatalytic performance. The resulting electrocatalyst displays good multiple electrocatalytic activities for carbon dioxide reduction, oxygen reduction, and evolution reactions, enabling the fabrication of integrated energy devices. Importantly, the CO 2 ‐H 2 O overall splitting with the as‐prepared electrocatalysts has been driven by the commercial solar cell and the zinc‐air battery assembled with the same catalyst respectively, showing high CO faradaic efficiency up to 90%. Especially, the overall solar‐to‐CO conversion efficiency is up to 13% and the corresponding utilization efficiency of solar‐to‐electricity can reach 54.4%, demonstrating the large promising space to chase the limit that solar cells can possibly achieve. This work provides new opportunities to modulate the atomic bridging structure of metal‐nitrogen‐carbon for integrated electrolysis.