Surface Engineering over Metal–Organic Framework Nanoarray to Realize Boosted and Sustained Urea Oxidation

Abstract Facilitating C─N bond cleavage and promoting *COO desorption are essential yet challenging in urea oxidation reactions (UORs). Herein a novel interfacial coordination assembly protocol is established to modify the Co‐phytate coordination complex on the Ni‐based metal–organic framework (MOF) nanosheet array (CC/Ni‐BDC@Co‐PA) toward boosted and sustained UOR electrocatalysis. Comprehensive experimental and theoretical investigations unveil that surface Co‐PA modification over Ni‐BDC can manipulate the electronic state of Ni sites, and in situ evolved charge‐redistributed surface can promote urea adsorption and the subsequent C─N bond cleavage. Impressively, Co‐PA functionalization can impart a negatively charged catalyst surface with improved aerophobicity, not only weakening *COO adsorption and promoting CO 2 departure, but also repelling CO 3 2− approaching to deactivate Ni species, eventually alleviating CO 2 poisoning and enhancing operational durability. Beyond that, improved hydrophilic and aerophobic characteristics would also contribute to better mass transfer kinetics. Consequently, CC/Ni‐BDC@Co‐PA exhibits prominent UOR performance with an ultralow potential of 1.300 V versus RHE to attain 10 mA cm −2 , a small Tafel slope of 45 mV dec −1 , and strong durability, comparable to the best Ni‐based electrocatalysts documented thus far. This work affords a novel paradigm to construct MOF‐based materials for promoted and sustained UOR catalysis through elegant surface engineering based on a metal‐PA complex.