Electron Bridge Enhanced Charge Polarization Enables Efficient and Ultra‐Long Stable Urea Electrosynthesis

ABSTRACT Urea electrosynthesis from carbon dioxide and nitrates powered by green electricity is a zero‐carbon route for urea production. Simultaneously achieving high activity and long‐term stability is a prerequisite for the industrialization of urea electrosynthesis. In this study, we propose an electron bridge strategy based on a Pd 1 and Ni 1 dual single‐atom alloy to boost the electrocatalytic activity and durability for urea electrosynthesis. The single‐atom Ni 1 sites act as electron bridges to promote charge transfer from Cu to Pd 1 sites, leading to charge‐polarized Pd–Cu sites, which upshift the d‐band center and improve oxidation resistance of the catalyst. Consequently, the Pd 1 and Ni 1 dual single‐atom sites simultaneously accelerates both carbon dioxide reduction and nitrates reduction half‐reactions, while facilitating the first C–N coupling step. The Pd 1 and Ni 1 dual single‐atom alloys deliver a urea yield rate of 541.6 mmol g cat −1 h −1 with a urea Faradaic efficiency of 57.3%. Remarkably, this catalyst achieves a record durability of 1700 h at a current density of 40 mA cm −2 . This work provides new insights into the synergistic catalysis of complex multi‐molecule reactions through cooperative multiple active sites.