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Electrochemical co-reduction of CO2 and nitrogen sources (N2 or NO3−) provides a promising route for ambient urea synthesis, yet suffers from low conversion efficiency or reliance on fossil fuel-derived NH3/NO3−. Herein, we present an integrated plasma-electrocatalytic route for sustainable urea synthesis from ambient air, which involves the initial plasma-driven air oxidation to form NOx− and followed by electrocatalytic co-reduction of CO2 + NOx− to produce urea. Specially, a bifunctional BiSA/a-MoO3 catalyst (isolated Bi single atom on amorphous MoO3) was designed to promote both plasma and electrocatalytic processes, consequently achieving the exceptional urea yield rate of 55.9 mmol·h−1·g−1 and Faradaic efficiency of 59.7%. The combined theoretical calculations and in situ spectroscopic measurements reveal the synergy of BiSA and unsaturated Mo sites in boosting the C–N coupling of *COOH and *NH2 intermediates for selective urea formation.

This is an open access article under the terms of the Creative Commons Attribution 4.0 International License (CC BY 4.0, https://creativecommons.org/licenses/by/4.0/).
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