Abstract
The direct electroreduction of CO2 at an electrolyte-free cathode to generate liquid chemical products with high concentration, selectivity and stability is highly desired, yet extremely challenging, and such systems are lacking. Here we report a high-flux membrane electrode assembly design that uses core–shell structural Cu/Bi nanowires grown on three-dimensional Cu foam with a mean pore size of 190 μm (3D-Cu/Bi) as the cathode. Benefiting from the abundant active sites and high permeability of 3D-Cu/Bi, the catholyte-free membrane electrode assembly-based electrolyser can directly convert CO2 into formate with a high concentration of 4.5 M and maintain a high Faradaic efficiency of ~90% for 8,000 h at 200 mA cm−2. We further demonstrate the continuous production of concentrated formate solution with a scaled-up 100 cm2 electrolyser at 20 A for over 2,000 h.
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All other data are available from the corresponding author upon request. Source data are provided with this paper.
References
De Luna, P. et al. What would it take for renewably powered electrosynthesis to displace petrochemical processes? Science 364, eaav3506 (2019).
Ozden, A. et al. Carbon-efficient carbon dioxide electrolysers. Nat. Sustain. 5, 563–573 (2022).
Fang, W. et al. Durable CO2 conversion in the proton-exchange membrane system. Nature 626, 86–91 (2024).
Jiao, J. et al. Constructing asymmetric double-atomic sites for synergistic catalysis of electrochemical CO2 reduction. Nat. Commun. 14, 6164 (2023).
Rong, X., Wang, H.-J., Lu, X.-L., Si, R. & Lu, T.-B. Control synthesis of vacancy-defect single-atom catalyst for boosting CO2 electroreduction. Angew. Chem. Int. Ed. 59, 1961–1965 (2020).
Wakerley, D. et al. Gas diffusion electrodes, reactor designs and key metrics of low-temperature CO2 electrolysers. Nat. Energy 7, 130–143 (2022).
Kibria, M. G. et al. Electrochemical CO2 reduction into chemical feedstocks: from mechanistic electrocatalysis models to system design. Adv. Mater. 31, 1807166 (2019).
Lv, J.-J. et al. Microenvironment engineering for the electrocatalytic CO2 reduction rreaction. Angew. Chem. Int. Ed. 61, e202207252 (2022).
Jouny, M., Luc, W. & Jiao, F. General techno-economic analysis of CO2 electrolysis systems. Ind. Eng. Chem. Res. 57, 2165–2177 (2018).
Chi, L.-P. et al. Stabilizing indium sulfide for CO2 electroreduction to formate at high rate by zinc incorporation. Nat. Commun. 12, 5835 (2021).
Bushuyev, O. S. et al. What should we make with CO2 and how can we make it? Joule 2, 825–832 (2018).
Wang, W.-H., Himeda, Y., Muckerman, J. T., Manbeck, G. F. & Fujita, E. CO2 hydrogenation to formate and methanol as an alternative to photo- and electrochemical CO2 reduction. Chem. Rev. 115, 12936–12973 (2015).
Álvarez, A. et al. Challenges in the greener production of formates/formic acid, methanol, and DME by heterogeneously catalyzed CO2 hydrogenation processes. Chem. Rev. 117, 9804–9838 (2017).
Zheng, T. et al. Copper-catalysed exclusive CO2 to pure formic acid conversion via single-atom alloying. Nat. Nanotechnol. 16, 1386–1393 (2021).
Fan, L., Xia, C., Zhu, P., Lu, Y. & Wang, H. Electrochemical CO2 reduction to high-concentration pure formic acid solutions in an all-solid-state reactor. Nat. Commun. 11, 3633 (2020).
Xia, C. et al. Continuous production of pure liquid fuel solutions via electrocatalytic CO2 reduction using solid-electrolyte devices. Nat. Energy 4, 776–785 (2019).
Zhu, P. & Wang, H. High-purity and high-concentration liquid fuels through CO2 electroreduction. Nat. Catal. 4, 943–951 (2021).
Wang, Z. et al. Carbon-confined indium oxides for efficient carbon dioxide reduction in a solid-state electrolyte flow cell. Angew. Chem. Int. Ed. 61, e202200552 (2022).
Fernández-Caso, K., Díaz-Sainz, G., Alvarez-Guerra, M. & Irabien, A. Electroreduction of CO2: advances in the continuous production of formic acid and formate. ACS Energy Lett. 8, 1992–2024 (2023).
Yang, H., Kaczur, J. J., Sajjad, S. D. & Masel, R. I. Performance and long-term stability of CO2 conversion to formic acid using a three-compartment electrolyzer design. J.CO2 Util. 42, 101349 (2020).
Zhang, Z. et al. Membrane electrode assembly for electrocatalytic CO2 reduction: principle and application. Angew. Chem. Int. Ed. 62, e202302789 (2023).
Ge, L. et al. Electrochemical CO2 reduction in membrane-electrode assemblies. Chem 8, 663–692 (2022).
Wang, Z. et al. Efficient electroconversion of carbon dioxide to formate by a reconstructed amino-functionalized indium–organic framework electrocatalyst. Angew. Chem. Int. Ed. 60, 19107–19112 (2021).
Li, W. et al. Bifunctional ionomers for efficient co-electrolysis of CO2 and pure water towards ethylene production at industrial-scale current densities. Nat. Energy 7, 835–843 (2022).
Wonhee, L., Eun, K. Y., Hye, Y. M., Kwan, J. S. & Tae, P. K. Catholyte-free electrocatalytic CO2 reduction to formate. Angew. Chem. Int. Ed. 57, 6883–6887 (2018).
Li, L. et al. Stable, active CO2 reduction to formate via redox-modulated stabilization of active sites. Nat. Commun. 12, 5223 (2021).
Bi, J. et al. High-rate CO2 electrolysis to formic acid over a wide potential window: an electrocatalyst comprised of indium nanoparticles on chitosan-derived graphene. Angew. Chem. Int. Ed. 62, e202307612 (2023).
Abdinejad, M. et al. Insertion of MXene-based materials into Cu–Pd 3D aerogels for electroreduction of CO2 to formate. Adv. Energy Mater. 13, 2300402 (2023).
Wan, Y. et al. Oxidation state modulation of bismuth for efficient electrocatalytic nitrogen reduction to ammonia. Adv. Funct. Mater. 31, 2100300 (2021).
Li, Z. et al. Electron-rich Bi nanosheets promote CO2⋅− formation for high-performance and pH-universal electrocatalytic CO2 reduction. Angew. Chem. Int. Ed. 62, e202217569 (2023).
Huang, J. E. et al. CO2 electrolysis to multicarbon products in strong acid. Science 372, 1074–1078 (2021).
Chi, L.-P. et al. Efficient and stable acidic CO2 electrolysis to formic acid by a reservoir structure design. Proc. Natl Acad. Sci. USA 120, e2312876120 (2023).
Li, Y. et al. Coupling CO2 reduction with CH3OH oxidation for efficient electrosynthesis of formate on hierarchical bifunctional CuSn alloy. Nano Energy 98, 107277 (2022).
Tang, J. et al. Advantages of eutectic alloys for creating catalysts in the realm of nanotechnology-enabled metallurgy. Nat. Commun. 10, 4645 (2019).
Jia, G. et al. Size effects of highly dispersed bismuth nanoparticles on electrocatalytic reduction of carbon dioxide to formic acid. J. Am. Chem. Soc. 145, 14133–14142 (2023).
Duan, Y.-X. et al. Boosting production of HCOOH from CO2 electroreduction via Bi/CeOx. Angew. Chem. Int. Ed. 60, 8798–8802 (2021).
Fan, J. et al. Large-area vertically aligned bismuthene nanosheet arrays from galvanic replacement reaction for efficient electrochemical CO2 conversion. Adv. Mater. 33, 2100910 (2021).
Xue, H., Zhao, Z.-H., Liao, P.-Q. & Chen, X.-M. “Ship-in-a-bottle” integration of ditin(IV) sites into a metal–organic framework for boosting electroreduction of CO2 in acidic electrolyte. J. Am. Chem. Soc. 145, 16978–16982 (2023).
Liang, S. et al. Sulfur changes the electrochemical CO2 reduction pathway over Cu electrocatalysts. Angew. Chem. Int. Ed. 62, e202310740 (2023).
Wang, T. et al. Halogen-incorporated Sn catalysts for selective electrochemical CO2 reduction to formate. Angew. Chem. Int. Ed. 62, e202211174 (2023).
Lin, L. et al. A nanocomposite of bismuth clusters and Bi2O2CO3 sheets for highly efficient electrocatalytic reduction of CO2 to formate. Angew. Chem. Int. Ed. 62, e202214959 (2023).
Lv, L. et al. Coordinating the edge defects of bismuth with sulfur for enhanced CO2 electroreduction to formate. Angew. Chem. Int. Ed. 62, e202303117 (2023).
Geng, Q. et al. Revolutionizing CO2 electrolysis: fluent gas transportation within hydrophobic porous Cu2O. J. Am. Chem. Soc. 146, 10599–10607 (2024).
Shi, R. et al. Efficient wettability-controlled electroreduction of CO2 to CO at Au/C interfaces. Nat. Commun. 11, 3028 (2020).
Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).
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).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. J. Chem, Phys. 132, 154104 (2010).
Acknowledgements
This work was supported by the National Key R&D Program of China (2022YFA1502902 to T.-B.L.) and the National Natural Science Foundation of China (22531007 to T.-B.L. and 22375146 to Z.-Y.Y.).
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Z.-Y.Y. and T.-B.L. conceived and designed the project. J.-J.L. performed the experiments, collected and analysed the data. H.-J.W. carried out the DFT calculationS. C.Z. performed the finite-element analysis. Y.L., J.J., L.-L.W., C.W., D.-C.Z. and Z.-Y.W. helped with analysing the results. J.-J.L., Z.-Y.Y. and T.-B.L. wrote and revised the paper.
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Production of formate with the 1 cm2 electrolyser.
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Production of formate with the 100 cm2 electrolyser.
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Li, JJ., Wang, HJ., Zhang, C. et al. A high-flux membrane electrode assembly for CO2 electroreduction to 4.5 M formate with over 8,000 h stability. Nat Catal (2026). https://doi.org/10.1038/s41929-026-01524-9
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DOI: https://doi.org/10.1038/s41929-026-01524-9
