Self-Reconstruction of Sulfate-Terminated Copper Oxide Nanorods for Efficient and Stable 5-Hydroxymethylfurfural Electrooxidation

The electrochemical 5-hydroxymethylfurfural oxidation reaction (HMFOR) has been regarded as a viable alternative to sustainable biomass valorization. However, the transformation of the catalysts under harsh electrooxidation conditions remains controversial. Herein, we confirm the self-construction of cuprous sulfide nanosheets (Cu₂S NSs) into sulfate-terminated copper oxide nanorods (CuO-SO₄^2- NRs) during the first-cycle of the HMFOR, which achieves a near-quantitative synthesis of 2,5-furandicarboxylic acid (FDCA) with a >99.9% yield and faradaic efficiency without deactivation in 15 successive cycles. Electrochemical impedance spectroscopies confirm that the surface SO₄^2- effectively reduces the onset potential for HMFOR, while in situ Raman spectroscopies identify a reversible transformation from Cu^II-O to Cu^III-OOH in HMFOR. Furthermore, density functional theory calculations reveal that the surface SO₄^2- weakens the Cu-OH bonds in CuOOH to promote the rate-determining step of its coupling with the C atom in HMF-H* resulting from HMF hydrogenation, which synergistically enhances the catalytic activity of CuO-SO₄^2- NRs toward HMF-to-FDCA conversion.