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

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.