Electrocatalytic urea synthesis from HCOOH and NO3− on Fe-Pd dual atoms

Conventional electrocatalytic urea synthesis via CO2+N2 or CO2+NO3− coelectrolysis generally suffers from poor reactants coactivation, low C–N coupling efficiency, and serious competing reactions. To overcome these limitations, we implement HCOOH+NO3− coelectrolysis to urea using a Fe-Pd dual-atom catalyst (Fe1Pd1-DAC). Operando spectroscopic measurements and theoretical computations collectively reveal that Pd1 selectively dehydrogenates HCOOH to *COOH, while Fe1 selectively activates NO3− to *NH2. Specifically, the spatial proximity and electrophilic-nucleophilic synergy of *COOH and *NH2 enable the high C–N coupling efficiency and well-suppressed competing reactions. Consequently, Fe1Pd1-DAC assembled in a flow cell delivers the unprecedented urea yield rate up to 448.1 mmol h−1 g−1 and Faradaic efficiency of 78.3% at an industrial-level current density of −215 mA cm−2, far outperforming those obtained from CO2+N2 or CO2+NO3− coelectrolysis. Further techno-economic analysis demonstrates Fe1Pd1-DAC as a promising catalyst for economically feasible urea production via HCOOH+NO3− coelectrolysis.