3D Hierarchical‐Architectured Nanoarray Electrode for Boosted and Sustained Urea Electro‐Oxidation

Exploring active and durable Ni-based materials with optimized electronic and architectural engineering to promote the urea oxidation reaction (UOR) is pivotal for the urea-related technologies. Herein a 3D self-supported hierarchical-architectured nanoarray electrode (CC/MnNi@NC) is proposed in which 1D N-doped carbon nanotubes (N-CNTs) with 0D MnNi nanoparticles (NPs) encapsulation are intertwined into 2D nanosheet aligned on the carbon cloth for prominently boosted and sustained UOR electrocatalysis. From combined experimental and theoretical investigations, Mn-alloying can regulate Ni electronic state with downshift of the d-band center, facilitating active Ni3+ species generation and prompting the rate-determining step (*COO intermediate desorption). Meanwhile, the micro/nano-hierarchical nanoarray configuration with N-CNTs encapsulating MnNi NPs can not only endow strong operational durability against metal corrosion/agglomeration and enrich the density of active sites, but also accelerate electron transfer, and more intriguingly, promote mass transfer as a result of desirable superhydrophilic and quasi-superaerophobic characteristics. Therefore, with such elegant integration of 0D, 1D and 2D motifs into 3D micro/nano-hierarchical architecture, the resulting CC/MnNi@NC can deliver admirable UOR performance, favorably comparable to the best-performing UOR electrocatalysts reported thus far. This work opens a fresh prospect in developing advanced electrocatalysts via electronic manipulation coupled with architectural engineering for various energy conversion technologies.