Abstract
Integration of efficient value-added electrochemical oxidation with hydrogen evolution reaction presents a promising sustainable route for both hydrogen energy and the electrochemical refinery industry. However, the serious competition of oxygen evolution reaction (OER) with targeted oxidation reactions at high current densities forms a substantial hurdle for industrial application. Here we report a straightforward approach to inhibit OER side reaction by introducing a trace amount of Cu2+ into the electrolyte for efficient glycerol oxidation reaction (GOR). Such a strategy enables improved Faradaic efficiency of glycerol to the target product formic acid from 62.2% (without Cu2+ addition) to 99.3% at a high current density of 800 mA cm−2. The underlying mechanism is that a reversible redox process of Cu2+/Cu+ fully suppresses the formation of OER-active-phase hydroxy peroxide on the surface of GOR-active Co3O4 catalyst. The current strategy also applies to other important electrochemical oxidation reactions, paving the way for developing efficient non-OER electrochemical oxidation reactions for various chemical conversion processes.
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All data are available within the paper, Supplementary Information and Source Data file. The data that support the findings of this study are available from the corresponding author on request. Source data are provided with this paper.
References
Tong, W. et al. Electrolysis of low-grade and saline surface water. Nat. Energy 5, 367–377 (2020).
Zhu, J. et al. Recent advances in electrocatalytic hydrogen evolution using nanoparticles. Chem. Rev. 120, 851–918 (2019).
Chen, D. et al. Ultralow Ru loading transition metal phosphides as high-efficient bifunctional electrocatalyst for a solar-to-hydrogen generation system. Adv. Energy Mater. 10, 2000814 (2020).
Fabbri, E. et al. Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting. Nat. Mater. 16, 925–931 (2017).
Jia, X. et al. Coupling ferrocyanide-sssisted PW/PB redox with efficient direct seawater electrolysis for hydrogen production. ACS Catal. 13, 3692–3701 (2023).
Wu, Z. et al. Non-noble-metal-based electrocatalysts toward the oxygen evolution reaction. Adv. Funct. Mater. 30, 1910274 (2020).
Zhang, J.-Y. et al. Anodic hydrazine oxidation assists energy-efficient hydrogen evolution over a bifunctional cobalt perselenide nanosheet electrode. Angew. Chem. Int. Ed. 57, 7649–7653 (2018).
Zeng, L. et al. Cooperative Rh–O5/Ni(Fe) site for efficient biomass upgrading coupled with H2 production. J. Am. Chem. Soc. 145, 17577–17587 (2023).
Lu, X. et al. Highly efficient electro-reforming of 5-hydroxymethylfurfural on vertically oriented nickel nanosheet/carbon hybrid catalysts: structure–function relationships. Angew. Chem. Int. Ed. 133, 14649–14656 (2021).
Mohan, K. et al. Unveiling cutting edge innovations in the catalytic valorization of biodiesel byproduct glycerol into value added products. ChemistrySelect 8, e202204501 (2023).
Han, X. et al. Electrocatalytic oxidation of glycerol to formic acid by CuCo2O4 spinel oxide nanostructure catalysts. ACS Catal. 10, 6741–6752 (2020).
Li, Y. et al. Nickel-molybdenum nitride nanoplate electrocatalysts for concurrent electrolytic hydrogen and formate productions. Nat. Commun. 10, 5335 (2019).
Qian, Q. et al. Electrochemical biomass upgrading coupled with hydrogen production under industrial-level current density. Adv. Mater. 35, 2300935 (2023).
Xu, Y. et al. Integrating electrocatalytic hydrogen generation with selective oxidation of glycerol to formate over bifunctional nitrogen-doped carbon coated nickel–molybdenum–nitrogen nanowire arrays. Appl. Catal. B 298, 120493 (2021).
Yu, X. et al. Hydrogen evolution linked to selective oxidation of glycerol over CoMoO4—a theoretically predicted catalyst. Adv. Energy Mater. 12, 2103750 (2022).
Pei, Y. et al. Glycerol oxidation-assisted electrochemical CO2 reduction for the dual production of formate. J. Mater. Chem. A 10, 1309–1319 (2022).
Ke, Z. et al. Solar-assisted co-electrolysis of glycerol and water for concurrent production of formic acid and hydrogen. J. Mater. Chem. A 9, 19975–19983 (2021).
Jia, X. et al. Amorphous Ni(III)-based sulfides as bifunctional water and urea oxidation anode electrocatalysts for hydrogen generation from urea-containing water. Appl. Catal. B 312, 121389 (2022).
Xu, F. et al. Revealing and optimizing the dialectical relationship between NOR and OER: cation vacancy engineering enables RuO2 with unanticipated high electrochemical nitrogen oxidation performance. Adv. Energy Mater. 13, 2300615 (2023).
Guo, M. et al. Pulsed electrocatalysis enabling high overall nitrogen fixation performance for atomically dispersed Fe on TiO2. Angew. Chem. Int. Ed. 62, e202217635 (2023).
Fan, L. et al. High entropy alloy electrocatalytic electrode toward alkaline glycerol valorization coupling with acidic hydrogen production. J. Am. Chem. Soc. 144, 7224–7235 (2022).
Li, S. et al. Reconstruction-induced NiCu-based catalysts towards paired electrochemical refining. Energy Environ. Sci. 15, 3004–3014 (2022).
He, Z. et al. Promoting biomass electrooxidation via modulating proton and oxygen anion deintercalation in hydroxide. Nat. Commun. 13, 3777 (2022).
Wang, Y. et al. Efficient electrocatalytic oxidation of glycerol via promoted OH* generation over single-atom-bismuth-doped spinel Co3O4. ACS Catal. 12, 12432–12443 (2022).
Zhu, Y. et al. Biphasic transition metal nitride electrode promotes nucleophile oxidation reaction for practicable hybrid water electrocatalysis. Adv. Funct. Mater. 33, 2300547 (2023).
Dong, L. et al. Regulating Ni site in NiV LDH for efficient electrocatalytic production of formate and hydrogen by glycerol electrolysis. Rare Met. 41, 1583–1594 (2022).
Oh, L. S. et al. How to change the reaction chemistry on nonprecious metal oxide nanostructure materials for electrocatalytic oxidation of biomass-derived glycerol to renewable chemicals. Adv. Mater. 35, 1583–1594 (2022).
Hu, Z., Yan, Q. & Wang, Y. Dynamic surface reconstruction of perovskite oxides in oxygen evolution reaction and its impacts on catalysis: a critical review. Mater. Today 34, 101800 (2023).
Gao, L. et al. Recent advances in activating surface reconstruction for the high-efficiency oxygen evolution reaction. Chem. Soc. Rev. 50, 8428–8469 (2021).
Zhou, D. et al. Mechanistic regulation by oxygen vacancies in structural evolution promoting electrocatalytic water oxidation. ACS Catal. 13, 4398–4408 (2023).
Zhang, R. et al. Tracking the role of defect types in Co3O4 structural evolution and active motifs during oxygen evolution reaction. J. Am. Chem. Soc. 145, 2271–2281 (2023).
Jung, S. et al. Mechanistic insights into ZIF-67-derived Ir-doped Co3O4@N-doped carbon hybrids as efficient electrocatalysts for overall water splitting using in situ Raman spectroscopy. Chem. Eng. J. 468, 143717 (2023).
Chen, X. et al. Ultrathin Co3O4 layers with large contact area on carbon fibers as high-performance electrode for flexible zinc–air battery integrated with flexible display. Adv. Energy Mater. 7, 1700779 (2017).
Reikowski, F. et al. Operando surface X-ray diffraction studies of structurally defined Co3O4 and CoOOH thin films during oxygen evolution. ACS Catal. 9, 3811–3821 (2019).
Ortiz Peña, N. et al. Morphological and structural evolution of Co3O4 nanoparticles revealed by in situ electrochemical transmission electron microscopy during electrocatalytic water oxidation. ACS Nano 13, 11372–11381 (2019).
Zhang, Y. et al. Electronic and vacancy engineering of Mo-RuCoOx nanoarrays for high-efficiency water splitting. Adv. Funct. Mater. 33, 2303073 (2023).
Xiao, Z. et al. Operando identification of the dynamic behavior of oxygen vacancy-rich Co3O4 for oxygen evolution reaction. J. Am. Chem. Soc. 142, 12087–12095 (2020).
Davó-Quiñonero, A. et al. New insights into the role of active copper species in CuO/cryptomelane catalysts for the CO-PROX reaction. Appl. Catal. B 267, 118372 (2020).
Fu, J. et al. Unveiling the interfacial species synergy in promoting CO2 tandem electrocatalysis in near-neutral electrolyte. J. Am. Chem. Soc. 146, 23625–23632 (2024).
Zhang, Y. et al. Coupling glucose-assisted Cu(I)/Cu(II) redox with electrochemical hydrogen production. Adv. Mater. 33, 2104791 (2021).
Pang, X. et al. Efficient electrocatalytic oxidation of 5-hydroxymethylfurfural coupled with 4-nitrophenol hydrogenation in a water system. ACS Catal. 12, 1545–1557 (2022).
Zhang, N. et al. Surface activation and Ni–S stabilization in NiO/NiS2 for efficient oxygen evolution reaction. Angew. Chem. Int. Ed. 61, e202207217 (2022).
Chen, J. et al. Water adsorption and oxidation at the Co3O4(110) surface. J. Phys. Chem. Lett. 3, 2808–2814 (2012).
Kim, J.-H. et al. Enhanced activity promoted by CeOx on a CoOx electrocatalyst for the oxygen evolution reaction. ACS Catal. 8, 4257–4265 (2018).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Anisimov, V. I., Zaanen, J. & Andersen, O. K. Band theory and Mott insulators: Hubbard U instead of Stoner I. Phys. Rev. B 44, 943–954 (1991).
Acknowledgements
We acknowledge the financial support from the National Natural Science Foundation of China (grant numbers 52425201 to G.L. and U23A20545 and 22072163 to W.Q.) and the Natural Science Foundation of Liaoning Province of China (grant numbers 2024JH3/50100016 to W.Q. and 2024-BSBA-40 to X.D.). We acknowledge Y. Yan from Institute of Metal Research, Chinese Academy of Sciences, and Shanghai Synchrotron Radiation Facility for their kind technical assistance. G.L. thanks the New Cornerstone Science Foundation for financial support through the XPLORER PRIZE.
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G.L. and W.Q. supervised the project. W.Q. and Y.L. conceived the idea. Y.L. prepared the samples and carried out the electrochemical experiments. L.Y. and J.L. conducted the theoretical computation. Y.L., X.Q., X.L., Y.Y., K.Q. and X.D. characterized the catalysts. Y.L., W.Q. and G.L. co-wrote the manuscript. All authors discussed the results and assisted during manuscript preparation.
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Nature Sustainability thanks Xiaotong Han, Shiguo Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Supplementary Information
Supplementary Figs. 1–34, Tables 1 and 2 and Notes 1–12.
Supplementary Video 1
GOR and Cu-GOR process.
Supplementary Video 2
Cu-GOR and HER process.
Source data
Source Data Fig. 2
Electrocatalytic performance data.
Source Data Fig. 3
In situ Raman spectra data.
Source Data Fig. 4
XPS spectra data, XRD pattern data, etc.
Source Data Fig. 5
Free energy data.
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Li, Y., Yin, L., Liu, J. et al. Efficient glycerol electro-oxidation at an industrial-level current density. Nat Sustain 8, 1524–1532 (2025). https://doi.org/10.1038/s41893-025-01653-2
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DOI: https://doi.org/10.1038/s41893-025-01653-2
