Abstract
The catalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid is a key step in the production of bio-based plastics but remains limited by sluggish multi-electron transfer kinetics across multiple reaction intermediates. In this study, we address this long-standing challenge by introducing a Mn-O-Co electron bridge within spinel CoMn2O4 to mediate and accelerate electron transfer. Through precise valence state regulation, we engineer a heterogeneous electron bridge dominated by Mn4+-O2--Co3+ linkages, enabling more efficient electron flow. Experimental characterization and theoretical calculations reveal that the incorporation of Mn4+ significantly enhances electron delocalization across the bridge. The empty eg orbitals of Mn4+ (t2g3eg0) serve as efficient electron acceptors, creating an energy-level gradient with Co3+ (t2g4eg2) that favors directional electron transfer. Simultaneously, Mn4+ strengthens metal-oxygen covalency, further improving electron mobility. This engineered electron bridge structure enables highly efficient cooperation across the full six-electron transfer pathway in 5-hydroxymethylfurfural oxidation, driven by a dynamic electron compensation mechanism. As a result, an 2,5-furandicarboxylic acid yield of 98.1% is achieved. This work offers a valuable theoretical foundation for understanding cooperative electron transfer in heterogeneous catalysis and provides a rational strategy for designing efficient electron bridge structures.
Data availability
All data generated in this study are provided in the Supplementary Information/Source Data. All data are available from corresponding author upon request. Source data are provided with this paper.
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Acknowledgements
We would like to express our sincere gratitude to the Institute of Sustainability for Chemicals, Energy and Environment (ISCE2), A*STAR, Singapore for their professional testing services and technical support. This work was also supported by the National Key Research and Development Program of China (2021YFA1501801, X.N.L., 2022YFB3805401, J.X.W.), the National Natural Science Foundation of China (No. 22278375, Z.T.H., 22279115, J.S.T.), and the Baima Lake Laboratory Joint Fund of Zhejiang Provincial Natural Science Foundation of China under Grant No. LBMHD26B060001 (Z.T.H.).
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Z.T.H., J.S.T., Y.W., and X.N.L. initiated this research project. G.H. and Z.T.H. designed the experiments, performed the experimental work, and drafted the manuscript. X.H.T. and Y.H.Z. conducted electron microscopy analyses. M.W.T. performed synchrotron radiation experiments. J.S.T. and N.O.Y. carried out the model construction and DFT calculations. J.L.L., M.H., J.X.W., D.P.C., and Z.Y.P. contributed to the discussion around the experimental findings. Z.T.H., G.H. and X.H.T. contributed equally to this work. All coauthors discussed the data.
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Hu, ZT., He, G., Tao, X. et al. Valence-tuned electron bridge enables high-yield multi-electron HMF oxidation over spinel catalysts. Nat Commun (2026). https://doi.org/10.1038/s41467-026-69615-6
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DOI: https://doi.org/10.1038/s41467-026-69615-6
