Regulating the Innocuity of Urea Electro-Oxidation via Cation-mediated Adsorption

Urea electrolysis is an emerging technology that bridges efficient wastewater treatment and hydrogen production with lower electricity costs. However, conventional Ni-based catalysts could easily overoxidize urea into the secondary contaminant NO_x ^- , and enhancing the innocuity of urea electrolysis remains a grand challenge to be achieved. Herein, we tailored the electrode-electrolyte interface of an unconventional cation effect on the anodic oxidation of urea to regulate its activity and selectivity. Smaller cations of Li⁺ were discovered to increase the Faradaic efficiency (FE) of the innocuous N₂ product from the standard value of ~15 % to 45 %, while decreasing the FEs of the over-oxidized NO_x ^- product from ~80 % to 46 %, pointing to a more sustainable process. The kinetic and computational analysis revealed the dominant residence of cations on the outer Helmholtz layer, which forms the interactions with the surface adsorbates. The Li⁺ hydration shells and rigid hydrogen bonding network interact strongly with the adsorbed urea to decrease its adsorption energy and subjection to C-N cleavage, thereby directing it toward the N₂ pathway. This work emphasizes the tuning of the interactions within the electrode-electrolyte interface for enhancing the efficiency and sustainability of electrocatalytic processes.