Kinetically matched C-N coupling toward efficient urea electrosynthesis enabled on copper single-atom alloy.

Chemical C-N coupling from CO 2 and NO 3 - , driven by renewable electricity, toward urea synthesis is an appealing alternative for Bosch-Meiser urea production. However, the unmatched kinetics in CO 2 and NO 3 - reduction reactions and the complexity of C- and N-species involved in the co-reduction render the challenge of C-N coupling, leading to the low urea yield rate and Faradaic efficiency. Here, we report a single-atom copper-alloyed Pd catalyst (Pd 4 Cu 1 ) that can achieve highly efficient C-N coupling toward urea electrosynthesis. The reduction kinetics of CO 2 and NO 3 - is regulated and matched by steering Cu doping level and Pd 4 Cu 1 /FeNi(OH) 2 interface. Charge-polarized Pd δ- -Cu δ+ dual-sites stabilize the key *CO and *NH 2 intermediates to promote C-N coupling. The synthesized Pd 4 Cu 1 -FeNi(OH) 2 composite catalyst achieves a urea yield rate of 436.9 mmol g cat. -1 h -1 and Faradaic efficiency of 66.4%, as well as a long cycling stability of 1000 h. In-situ spectroscopic results and theoretical calculation reveal that atomically dispersed Cu in Pd lattice promotes the deep reduction of NO 3 - to *NH 2 , and the Pd-Cu dual-sites lower the energy barrier of the pivotal C-N coupling between *NH 2 and *CO.