Cu-tuned bifunctional CoMoP catalysts for electrocatalytic oxidation of 5-hydroxymethylfurfural and Co-production of hydrogen

The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) for the green production of bio-based 2,5-furandicarboxylic acid (FDCA) and hydrogen offers a sustainable pathway for utilizing biomass resources efficiently, in which the design and fabrication of electrocatalysts with tuned structure and properties is the key yet remains a big challenge. Herein, we report on the synthesis of Nickel foam supported CoMoP electrocatalysts with tuned electronic structure and enhanced adsorption capacity for HMF via a Cu-regulation strategy by making use of hydrothermal and low-temperature phosphating method (Cu@CoMoP/NF). The as-made Cu@CoMoP/NF catalysts were shown to be active for the electrocatalytic oxidation of HMF and the simultaneous production of hydrogen. The HMF oxidation reaction (HMFOR) coupled with the hydrogen evolution reaction occurs at a low cell voltage of 0.94 V at a current density of 10 mA cm -2 achieving 100% HMF conversion and 99.57% yeild of FDCA. It has been found that copper plays a critical role in Cu@CoMoP/NF, where Cu sites exhibit a marked electron-withdrawing behavior, promoting excited-state electron delocalization and inducing an upward shift in the d-band center. The coordinated electronic effects synergistically enhance the HMF adsorption at active sites while substantially lowering the kinetic barrier for subsequent transformations. This work may provide a promising strategy for the HMFOR and hydrogen production over Cu-tuned electrocatalysts and beyond. Cu@CoMoP/NF, engineered through a copper-modulation strategy to optimize its electronic structure and enhance HMF adsorption capacity, was synthesized and employed for the electrochemical oxidation of HMF to produce FDCA, enabling synergistic hydrogen generation. The HMFOR achieves a current density of 100 mA cm -2 at 1.29 V vs. RHE. In comparison, the HER reaches 10 mA cm -2 with an overpotential of 114 mV. This process demonstrates complete HMF conversion (100%), a 99.57% FDCA yield and a FE of 99.86%. Furthermore, the integrated HMFOR‖HER system exhibits significantly enhanced energy efficiency, requiring 470 mV less potential at 10 mA cm -2 compared to a conventional OER‖HER configuration. • Cu tuned the electronic structure of CoMoP catalysts for efficient oxidation of 5-hydroxymethylfurfural (HMF) coupled with hydrogen production (HER). • Cu functions to up-shift the d-band center of CoMoP and increases the HMF adsorption strength. • The HMF oxidation takes place at a current density of 100 mA cm -2 at 1.29 V vs. RHE and the HER at 10 mA cm -2 at an overpotential of 114 mV. • The HMF conversion is 100%, the FDCA yield is 99.6% and the F.E. is 99.8%. • The HMFOR‖HER is energy-effective, of which potential at 10 mA cm -2 is reduced by 470 mV in comparison with OER‖HER.