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

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 Pd1 and Ni1 dual single-atom alloy to boost the electrocatalytic activity and durability for urea electrosynthesis. The single-atom Ni1 sites act as electron bridges to promote charge transfer from Cu to Pd1 sites, leading to charge-polarized Pd-Cu sites, which upshift the d-band center and improve oxidation resistance of the catalyst. Consequently, the Pd1 and Ni1 dual single-atom sites simultaneously accelerates both carbon dioxide reduction and nitrates reduction half-reactions, while facilitating the first C-N coupling step. The Pd1 and Ni1 dual single-atom alloys deliver a urea yield rate of 541.6 mmol gcat -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.