Efficient Urea Electrosynthesis on a Cu ₃ Molecular Catalyst with Dynamically Adaptive Intercopper Spacings

Electrocatalytic urea synthesis from carbon monoxide (CO) and nitrate ions (NO₃^-) represents a promising alternative to the conventional energy-intensive industrial methods, while this approach is strongly limited by the kinetically sluggish C-N coupling process and the competing side reactions. Herein, we report a trinuclear-copper molecular catalyst (denoted as Cu₃-flex) that can enable dynamic and self-adaptive intercopper spacings among those triangular-shaped Cu₃ adjacent sites upon the binding of two *CO and one *NO₃^-. The dynamic variation of the intercopper spacings induced by the bridged *CO adsorption allows us to promote the first C-N coupling of *CO and *N to form the key *NCO intermediate, as well as the subsequent capturing of another *NO₃^- and the second C-N coupling to produce urea. The Cu₃-flex catalyst exhibited a high urea electrosynthesis performance for the coreduction of CO and NO₃^-, including a urea production rate of 122 mmol·g_cat.^-1·h^-1, a Faradaic efficiency of 69%, and a notable electrochemical stability of >125 h.