Highly Selective Electroreduction N2 and CO2 to Urea over Artificial Frustrated Lewis Pairs

Simultaneously electrocatalytic conversion of N2 and CO2 into value-added urea is highly anticipated but suffers from the predicament of destitute chemisorption, activation and coupling activity of reactant molecules. Herein, the unique frustrated Lewis pairs (FLPs) are precisely designed in flower-like nickel borate [Ni3(BO3)2], where the surface hydroxyl and neighboring Ni site serve as Lewis base and acid, respectively. Comprehensive investigations endorse that Lewis basic and acidic sites in FLPs act synergistically to targeted capture inert CO2 and N2 by orbital interaction. Subsequently, the bonding and antibonding orbitals of inert gas interact with the empty orbitals of Lewis acid and nonbonding orbitals of Lewis base, respectively, achieving the molecule activation by FLPs. Afterwards, the *N=N* and CO intermediates undergo electrocatalytic C-N coupling by the σ orbital carbonylation strategy to produce *NCON* precursors. Thus, Ni3(BO3)2-150 nanocrystal deliver the record-highest urea yield rate of 9.70 mmol h-1 g-1 and Faradaic efficiency of 20.36 % at -0.5 V vs. RHE.