Platinum-Copper Dual-Atom Catalyst Enables the Selective Electro-Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid

Abstract

The electrochemical hydroxymethylfurfural oxidation reaction (HMFOR) has emerged as a sustainable strategy for producing high-value chemicals, yet achieving high product selectivity remains a key challenge. Herein, we report the electrochemical conversion of HMF into 2,5-furandicarboxylic acid (FDCA) under alkaline conditions over a catalyst with a high density of Pt-Cu dual-atom sites supported on N,S-doped carbon nanosheets (Pt-Cu_high/NSC). At a low Pt loading of 0.74 wt.%, the Pt-Cu_high/NSC catalyst demonstrates excellent HMFOR activity in 0.1 M KOH, including a low activation potential (0.98 V), high current output (1006.4 mA mg⁻¹ at 1.42 V), excellent FDCA selectivity (97.4%), high Faradaic efficiency (97.6%), and long-term operational stability. These metrics surpass most previously reported catalyst systems. In comparison, a monometallic catalyst with only Cu single atom sites (Cu/NSC) showed low selectivity towards FDCA during HMFOR, instead favouring the production of 5-formyl-2-furancarboxylic (FFCA, 81.6% yield). A Pt/NSC catalyst showed negligible activity for HMFOR. Experimental data and theoretical calculations for Pt-Cu_high/NSC reveal that Pt sites facilitate OH⁻ adsorption, which in turn promotes deeper oxidation of FFCA on adjacent Cu sites. This study encourages the wider pursuit of dual-atom catalysts (DACs) for the HMFOR and other challenging electrochemical syntheses.

Keywords

2,5-furandicarboxylic acid / Dual-atom catalyst / Electrocatalytic biomass upgrading / Hydroxymethylfurfural oxidation reaction / OH⁻ and HMF adsorption sites

References

[1] Y. Li, H. Huang, M. Jiang, et al., “Advancements in Transition Bimetal Catalysts for Electrochemical 5-Hydroxymethylfurfural (HMF) Oxidation,” Journal of Energy Chemistry 98 (2024): 24-46.

[2] B. Chen, Q. Hou, R. Smith, X. Qi, and H. Guo, “Electrocatalytic Oxidation of Biomass-Derived Furans to 2,5-furandicarboxylic Acid—A Review,” Green Chemistry 27 (2025): 8414-8447.

[3] Y. Duan, X. Lu, O. Fan, et al., “Non-Noble Metal Catalysts for Electrooxidation of 5-Hydroxymethylfurfural,” Chemsuschem 18 (2025): 3.

[4] P. Zhu, M. Shi, Z. Shen, X. Liao, and Y. Chen, “Electrocatalytic Conversion of Biomass-Derived Furan Compounds: Mechanisms, Catalysts and Perspectives,” Chemical Science 15 (2024): 4723-4756.

[5] C. Chen, M. Lv, H. Hu, et al., “5-Hydroxymethylfurfural and Its Downstream Chemicals: A Review of Catalytic Routes,” Advanced Materials 36 (2024): 37.

[6] M. Huddleston and Y. Sun, “Biomass Valorization via Paired Electrocatalysis,” Chemsuschem 18 (2025): 8.

[7] A. Yadav and S. Dutta, “Effect of Single-Metal-Atoms in Electrovalorization of Biomass and Paired Electrolysis,” Chemical Engineering Journal 494 (2024): 152950.

[8] Y. Hu, T. Chao, Y. Dou, Y. Xiong, X. Liu, and D. Wang, “Isolated Metal Centers Activate Small Molecule Electrooxidation: Mechanisms and Applications,” Advanced Materials 37 (2025): 2418504.

[9] T. Wang, L. Tao, X. Zhu, et al., “Combined Anodic and Cathodic Hydrogen Production from Aldehyde Oxidation and Hydrogen Evolution Reaction,” Nature Catalysis 5, no. 1 (2022): 66-73.

[10] J. Lei, H. Zhang, J. Yang, et al., “Structural Designs and Mechanism Insights into Electrocatalytic Oxidation of 5-Hydroxymethylfurfural,” Journal of Energy Chemistry 100 (2025): 792-814.

[11] X. Pang, H. Bai, H. Zhao, W. Fan, and W. Shi, “Efficient Electrocatalytic Oxidation of 5-Hydroxymethylfurfural Coupled with 4-Nitrophenol Hydrogenation in a Water System,” ACS Catalysis 12, no. 2 (2022): 1545-1557.

[12] C. Chen, L. Wang, B. Zhu, et al., “2,5-Furandicarboxylic Acid Production via Catalytic Oxidation of 5-hydroxymethylfurfural: Catalysts, Processes and Reaction Mechanism,” Journal of Energy Chemistry 54 (2021): 528-554.

[13] Y. Lu, T. Liu, C.-L. Dong, et al., “Tailoring Competitive Adsorption Sites by Oxygen-Vacancy on Cobalt Oxides to Enhance the Electrooxidation of Biomass,” Advanced Materials 34, no. 2 (2022).

[14] S. A. Akhade, N. Singh, O. Y. Gutiérrez, et al., “Electrocatalytic Hydrogenation of Biomass-Derived Organics: A Review,” Chemical Reviews 120, no. 20 (2020): 11370-11419.

[15] J.-X. Wu, W.-X. Chen, C.-T. He, et al., “Atomically Dispersed Dual-Metal Sites Showing Unique Reactivity and Dynamism for Electrocatalysis,” Nano-Micro Letters 15, no. 1 (2023): 120.

[16] M. Li, H. Sun, C. Wang, et al., “Balancing Competitive Adsorption on Co₃O₄@P, N-Doped Porous Carbon to Enhance the Electrocatalytic Upgrading of Biomass Derivatives,” Small 21 (2025): 6.

[17] M. Padligur, P. Westerfeld, J. Linkhorst, and M. Wessling, “Electrochemical Oxidation of 5-Hydroxymethylfurfural with Flow Electrodes: A Novel Approach for Continuous Synthesis of 2,5-Furandicarboxylic Acid,” Chemical Engineering Journal 504 (2025): 158374.

[18] L. Shi, W. Cai, F. Zhang, et al., “Engineering Oxygen Intermediates Adsorption on Amorphous NiFe Alloys for Highly Active and Selective Electrochemical Biomass Conversion,” Angewandte Chemie International Edition 64 (2025): 18.

[19] X. Jiang, W. Li, Y. Liu, et al., “Electrocatalytic Oxidation of 5-Hydroxymethylfurfural for Sustainable 2,5-Furandicarboxylic Acid Production—From Mechanism to Catalysts Design,” SusMat 3 (2023): 21-43.

[20] T. Ennaert, J. Van Aelst, J. Dijkmans, et al., “Potential and Challenges of Zeolite Chemistry in the Catalytic Conversion of Biomass,” Chemical Society Reviews 45, no. 3 (2016): 584-611.

[21] H. Zhao, D. Lu, J. Wang, et al., “Raw Biomass Electroreforming Coupled to Green Hydrogen Generation,” Nature Communications 12, no. 1 (2021): 2008.

[22] P. Prabhu, Y. Wan, and J.-M. Lee, “Electrochemical Conversion of Biomass Derived Products into High-value Chemicals,” Matter 3, no. 4 (2020): 1162-1177.

[23] X. Jiang, X. Ma, Y. Liu, et al., “Cation Vacancies Creation Propel Pre-Oxidation Enhancing Nickel Hydroxide Activity for Highly Efficient 5-hydroxymethylfurfural Upgrading,” Applied Catalysis B: Environment and Energy 347 (2024): 123785.

[24] Z. Yang, S. Wang, C. Wei, L. Chen, Z. Xue, and T. Mu, “Proton Transfer Mediator for Boosting the Current Density of Biomass Electrooxidation to the Ampere Level,” Energy & Environmental Science 17 (2024): 1603-1611.

[25] C. Li, F. Wang, Y. Nie, et al., “Ionic Liquid Dopant Induced 3D Hierarchical CuO Nanostructures with Doped Heteroatoms and Highly Dispersed Ag for Electrochemical Upgrading of 5-Hydroxymethylfurfural,” Chemical Engineering Journal 481 (2024): 148580.

[26] Y. Wu, L. Ma, J. Wu, M. Song, C. Wang, and J. Lu, “High-Surface Area Mesoporous Sc 2 O 3 with Abundant Oxygen Vacancies as New and Advanced Electrocatalyst for Electrochemical Biomass Valorization,” Advanced Materials 36 (2024): 2311698.

[27] L. Gloag, S. V. Somerville, J. J. Gooding, and R. D. Tilley, “Co-catalytic Metal-Support Interactions in Single-Atom Electrocatalysts,” Nature Reviews Materials 9 (2024): 173-189.

[28] R.-J. Van Putten, J. C. Van Der Waal, and J. E. De, “Hydroxymethylfurfural, a Versatile Platform Chemical Made from Renewable Resources,” Chemical Reviews 113, no. 3 (2013): 1499-1597.

[29] L. Guo, X. Zhang, L. Gan, et al., “Advances in Selective Electrochemical Oxidation of 5-Hydroxymethylfurfural to Produce High-Value Chemicals,” Advanced Science 10, no. 4 (2023): 2205540.

[30] Y. Gao, L. Ge, H. Xu, K. Davey, Y. Zheng, and S.-Z. Qiao, “Electrocatalytic Refinery of Biomass-Based 5-Hydroxymethylfurfural to Fine Chemicals,” ACS Catalysis 13, no. 17 (2023): 11204-11231.

[31] Y. Yang, W. H. Lie, R. R. Unocic, et al., “Defect-Promoted Ni-Based Layer Double Hydroxides with Enhanced Deprotonation Capability for Efficient Biomass Electrooxidation,” Advanced Materials 35, no. 48 (2023): 2305573.

[32] Y. Qiang, D. Ouyang, L. You, D. Liu, and X. Zhao, “Liquid Flow Fuel Cell with an Electrodeposition-Modified Nickel Foam Anode for Efficient Oxidation of 5-Hydroxymethylfurfural to Produce 2, 5-furandicarboxylic Acid with Co-Generation of Electricity,” Chemical Engineering Journal 469 (2023): 143832.

[33] C. Liu, X.-R. Shi, K. Yue, et al., “S-Species-Evoked High-Valence Ni 2+δ of the Evolved β-Ni(OH) 2 Electrode for Selective Oxidation of 5-Hydroxymethylfurfural,” Advanced Materials 35, no. 12 (2023): 2211177.

[34] H. Xu, G. Xin, W. Hu, et al., “Single-Atoms Ru/NiFe Layered Double Hydroxide Electrocatalyst: Efficient for Oxidation of Selective Oxidation of 5-Hydroxymethylfurfural and Oxygen Evolution Reaction,” Applied Catalysis B: Environmental 339 (2023): 123157.

[35] G. Liu, T. Nie, Z. Song, et al., “Pd Loaded NiCo Hydroxides for Biomass Electrooxidation: Understanding the Synergistic Effect of Proton Deintercalation and Adsorption Kinetics,” Angewandte Chemie International Edition 62, no. 45 (2023): e202311696.

[36] X. Guo, H. Fu, J. Yang, et al., “Promoting Electrocatalytic Hydrogenation of 5-Hydroxymethylfurfural over a Cooperative Ag/SnO₂ Catalyst in a Wide Potential Window,” ACS Catalysis 13, no. 20 (2023): 13528-13539.

[37] X. Lu, K.-H. Wu, B. Zhang, et al., “Highly Efficient Electro-Reforming of 5-Hydroxymethylfurfural on Vertically Oriented Nickel Nanosheet/Carbon Hybrid Catalysts: Structure-Function Relationships,” Angewandte Chemie International Edition 60, no. 26 (2021): 14528-14535.

[38] N. Zhang, Y. Zou, L. Tao, et al., “Electrochemical Oxidation of 5-Hydroxymethylfurfural on Nickel Nitride/Carbon Nanosheets: Reaction Pathway Determined by in Situ Sum Frequency Generation Vibrational Spectroscopy,” Angewandte Chemie International Edition 58, no. 44 (2019): 15895-15903.

[39] Y. Lu, C.-L. Dong, Y.-C. Huang, et al., “Identifying the Geometric Site Dependence of Spinel Oxides for the Electrooxidation of 5-Hydroxymethylfurfural,” Angewandte Chemie International Edition 59, no. 43 (2020): 19215-19221.

[40] B. You, N. Jiang, X. Liu, and Y. Sun, “Simultaneous H 2 Generation and Biomass Upgrading in Water by an Efficient Noble-Metal-Free Bifunctional Electrocatalyst,” Angewandte Chemie International Edition 55, no. 34 (2016): 9913-9917.

[41] X. Jiang, X. Ma, Y. Yang, et al., “Enhancing the Electrocatalytic Oxidation of 5-hydroxymethylfurfural through Cascade Structure Tuning for Highly Stable Biomass Upgrading,” Nano-Micro Letters 16 (2024): 275.

[42] J. Wu, J. Chen, T. Yu, et al., “Boosting Electrochemical Kinetics of NiCo₂ via MoO₂ Modification for Biomass Upgrading Assisted Hydrogen Evolution,” ACS Catalysis 13, no. 20 (2023): 13257-13266.

[43] Y. Sun, J. Wang, Y. Qi, W. Li, and C. Wang, “Efficient Electrooxidation of 5-Hydroxymethylfurfural Using Co-Doped Ni 3 S 2 Catalyst: Promising for H 2 Production Under Industrial-Level Current Density,” Advanced Science 9, no. 17 (2022): 2200957.

[44] J. J. Bozell and G. R. Petersen, “Technology Development for the Production of Biobased Products from Biorefinery Carbohydrates—the US Department of Energy's “Top 10” Revisited,” Green Chemistry 12, no. 4 (2010): 539.

[45] X. Jiang, P. Wang, Y. Zhang, L. Zhao, Y. Yang, and Y. Liu, “Highly Active Cobalt Oxide-Palladium Nanohybrid Catalyst Enables Selective Electrocatalytic Synthesis of Glycolic Acid,” Chemical Engineering Journal 502 (2024): 157962.

[46] Z. Fan, Q. Yang, W. Zhang, et al., “Self-Reconstruction of Sulfate-Terminated Copper Oxide Nanorods for Efficient and Stable 5-Hydroxymethylfurfural Electrooxidation,” Nano Letters 23, no. 23 (2023): 11314-11322.

[47] B. Zhu, C. Chen, L. Huai, Z. Zhou, L. Wang, and J. Zhang, “2,5-Bis(hydroxymethyl)furan: A New Alternative to HMF for Simultaneously Electrocatalytic Production of FDCA and H₂ over CoOOH/Ni Electrodes,” Applied Catalysis B: Environmental 297 (2021): 120396.

[48] C. Tang, Y. Zheng, M. Jaroniec, and S.-Z. Qiao, “Electrocatalytic Refinery for Sustainable Production of Fuels and Chemicals,” Angewandte Chemie International Edition 60, no. 36 (2021): 19572-19590.

[49] Y. Yang and T. Mu, “Electrochemical Oxidation of Biomass Derived 5-hydroxymethylfurfural (HMF): Pathway, Mechanism, Catalysts and Coupling Reactions,” Green Chemistry 23, no. 12 (2021): 4228-4254.

[50] Y. Zhou, T. J. A. Slater, X. Luo, and Y. Shen, “A Versatile Single-copper-atom Electrocatalyst for Biomass Valorization,” Applied Catalysis B: Environmental 324 (2023): 122218.

[51] J. Li, R. Qiu, S. Zhang, et al., “Synergistically Enhanced Co-Adsorption of Reactant and Hydroxyl on Platinum-Modified Copper Oxide for High-Performance HMF Oxidation,” Advanced Materials 37 (2025): 2417684.

[52] X. Deng, G.-Y. Xu, Y.-J. Zhang, et al., “Understanding the Roles of Electrogenerated Co 3+ and Co 4+ in Selectivity-Tuned 5-Hydroxymethylfurfural Oxidation,” Angewandte Chemie International Edition 60, no. 37 (2021): 20535-20542.

[53] L. Guo, X. Zhang, L. Gan, et al., “Advances in Selective Electrochemical Oxidation of 5-Hydroxymethylfurfural to Produce High-Value Chemicals,” Advanced Science 10 (2023): 2205540.

[54] R. Ge, Y. Wang, Z. Li, et al., “Selective Electrooxidation of Biomass-Derived Alcohols to Aldehydes in a Neutral Medium: Promoted Water Dissociation over a Nickel-Oxide-Supported Ruthenium Single-Atom Catalyst,” Angewandte Chemie 134 (2022): e202200211.

[55] A. R. C. Bredar, A. L. Chown, A. R. Burton, and B. H. Farnum, “Electrochemical Impedance Spectroscopy of Metal Oxide Electrodes for Energy Applications,” ACS Applied Energy Materials 3, no. 1 (2020): 66-98.

[56] H.-Y. Wang, S.-F. Hung, H.-Y. Chen, T.-S. Chan, H. M. Chen, and B. Liu, “In Operando Identification of Geometrical-Site-Dependent Water Oxidation Activity of Spinel Co₃O₄,” Journal of the American Chemical Society 138, no. 1 (2016): 36-39.

[57] N. Heidary and N. Kornienko, “Electrochemical Biomass Valorization on Gold-Metal Oxide Nanoscale Heterojunctions Enables Investigation of Both Catalyst and Reaction Dynamics with Operando Surface-Enhanced Raman Spectroscopy,” Chemical Science 11, no. 7 (2020): 1798-1806.

[58] L. Gao, Z. Liu, J. Ma, et al., “NiSe@NiO_x Core-Shell Nanowires as a Non-Precious Electrocatalyst for Upgrading 5-Hydroxymethylfurfural into 2,5-Furandicarboxylic Acid,” Applied Catalysis B: Environmental 261 (2020): 118235.

[59] Z. Zhou, C. Chen, M. Gao, B. Xia, and J. Zhang, “In Situ Anchoring of a Co₃O₄ Nanowire on Nickel Foam: An Outstanding Bifunctional Catalyst for Energy-Saving Simultaneous Reactions,” Green Chemistry 21, no. 24 (2019): 6699-6706.

[60] B. J. Taitt, D.-H. Nam, and K.-S. Choi, “A Comparative Study of Nickel, Cobalt, and Iron Oxyhydroxide Anodes for the Electrochemical Oxidation of 5-Hydroxymethylfurfural To 2,5-Furandicarboxylic Acid,” ACS Catalysis 9, no. 1 (2018): 660-670.

[61] M. J. Kang, H. Park, J. Jegal, S. Y. Hwang, Y. S. Kang, and H. G. Cha, “Electrocatalysis of 5-Hydroxymethylfurfural at Cobalt Based Spinel Catalysts with Filamentous Nanoarchitecture in Alkaline Media,” Applied Catalysis B: Environmental 242 (2019): 85-91.

[62] D.-H. Nam, B. J. Taitt, and K.-S. Choi, “Copper-based Catalytic Anodes to Produce 2,5-Furandicarboxylic Acid, a Biomass-Derived Alternative to Terephthalic Acid,” ACS Catalysis 8, no. 2 (2018): 1197-1206.

[63] M. Cai, S. Ding, B. Gibbons, X. Yang, M. C. Kessinger, and A. J. Morris, “Nickel(II)-Modified Covalent-Organic Framework Film for Electrocatalytic Oxidation of 5-hydroxymethylfurfural (HMF),” Chemical Communications 56, no. 92 (2020): 14361-14364.

[64] M. J. Kang, H. J. Yu, H. S. Kim, and H. G. Cha, “Deep Eutectic Solvent Stabilised Co-P Films for Electrocatalytic Oxidation of 5-Hydroxymethylfurfural into 2,5-Furandicarboxylic Acid,” New Journal of Chemistry 44, no. 33 (2020): 14239-14245.

[65] C. Yang, C. Wang, L. Zhou, et al., “Refining D-Band Center in Ni_0.85Se by Mo Doping: A Strategy for Boosting Hydrogen Generation via Coupling Electrocatalytic Oxidation 5-Hydroxymethylfurfural,” Chemical Engineering Journal 422 (2021): 130125.

[66] W. Wang, F. Kong, Z. Zhang, L. Yang, and M. Wang, “Sulfidation of Nickel Foam with Enhanced Electrocatalytic Oxidation of 5-Hydroxymethylfurfural To 2,5-Furandicarboxylic Acid,” Dalton Transactions 50, no. 31 (2021): 10922-10927.

[67] Y. Lu, C.-L. Dong, Y.-C. Huang, et al., “Identifying the Geometric Site Dependence of Spinel Oxides for the Electrooxidation of 5-Hydroxymethylfurfural,” Angewandte Chemie International Edition 59 (2020): 19215-19221.

[68] L. Gao, Y. Bao, S. Gan, et al., “Hierarchical Nickel-Cobalt-Based Transition Metal Oxide Catalysts for the Electrochemical Conversion of Biomass into Valuable Chemicals,” Chemsuschem 11, no. 15 (2018): 2547-2553.

[69] M. Zhang, Y. Liu, B. Liu, Z. Chen, H. Xu, and K. Yan, “Trimetallic NiCoFe-Layered Double Hydroxides Nanosheets Efficient for Oxygen Evolution and Highly Selective Oxidation of Biomass-Derived 5-hydroxymethylfurfural,” ACS Catalysis 10, no. 9 (2020): 5179-5189.

[70] R. Latsuzbaia, R. Bisselink, A. Anastasopol, et al., “Continuous Electrochemical Oxidation of Biomass Derived 5-(Hydroxymethyl)furfural into 2,5-Furandicarboxylic Acid,” Journal of Applied Electrochemistry 48, no. 6 (2018): 611-626.

RIGHTS & PERMISSIONS

2025 The Author(s). SusMat published by Sichuan University and John Wiley & Sons Australia, Ltd.