CoP Nanoparticle Confined in P, N Co‐Doped Porous Carbon Anchored on P‐Doped Carbonized Wood Fibers with Tailored Electronic Structure for Efficient Urea Electro‐Oxidation

Abstract Electronic structure optimization and architecture modulation are widely regarded as rational strategies to enhance the electrocatalysts catalytic performance. Herein, a hybridization of ZIF‐67‐derived CoP nanoparticles embedded in P, N co‐doped carbon matrix (PNC) and anchored on P‐doped carbonized wood fibers (PCWF) is constructed using a simple simultaneous phosphorization and carbonization strategy. Benefiting from the optimized surface/interface electronic structures, abundant exposed active sites, and outstanding conductivity, the CoP@PNC/PCWF can drive the urea oxidation reaction (UOR) with greater activity and better stability than most recently reported electrocatalysts, in which a potential as low as 1.32 V (vs reversible hydrogen electrode, RHE) is needed to reach 50 mA cm^‐2 and shows excellent durability. Furthermore, for overall urea splitting, using the CoP@PNC/PCWF electrocatalyst as the anode and commercial Pt/C supported on nickel foam as the cathode, an ultralow cell voltage of 1.50 V (vs RHE) is expected to achieve the 50 mA cm^‐2 and operate continuously for more than 50 h at 20 mA cm^‐2. The reported strategy may shed light on the use of renewable resources to design and synthesize high‐performance non‐Ni‐based phosphides UOR electrocatalysts for energy‐saving H₂ production.