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 Co 3 O 4 (Co 3 O 4 @PNC). Co-doping with these two heteroatoms generates C 3 P = 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, Co 3 O 4 @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.