Balancing Competitive Adsorption on Co₃O₄@P, N‐Doped Porous Carbon to Enhance the Electrocatalytic Upgrading of Biomass Derivatives

Abstract The electrocatalytic oxidation of 5‐hydroxymethylfurfural (HMF) represents an environmentally friendly approach to generate high‐value‐added chemicals from biomass. The successful electrochemical transformation of HMF during the oxidation reaction (HMFOR) necessitates an ideal adsorption interaction between HMF and OH⁻ on the electrode surface. Yet, catalysts with a singular active site offer limited flexibility in managing the competitive adsorption of HMF and OH⁻. To this end, different active sites are customized in this work to construct a P and N co‐doped porous carbon that wrapped Co₃O₄ (Co₃O₄@PNC). Co‐doping with these two heteroatoms generates C₃P = O and pyrrolic N as adsorption sites to better balance the adsorption of HMF and OH⁻, respectively, rather than promoting competition between the HMF and OH⁻ on a single active site. With this design strategy, Co₃O₄@PNC demonstrates significant HMFOR activity, the conversion rate of HMF surpassed 99% with a 2,5‐furandicarboxylic acid (FDCA) yield exceeding 95% after 2 h of electrolysis. Furthermore, it shows universal applicability in the electrooxidation of other alcohol/aldehyde substrates, yielding efficiencies of 90–99%. This work not only provides guidance for advanced electrocatalysts design toward alcohol/aldehyde oxidation but also offers insights into the utilization of biomass‐derived platform chemicals.