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Scalable synthesis of Cu-cluster catalysts via spark ablation for the electrochemical conversion of CO2 to acetaldehyde

Nature Synthesis volume 4, pages 336–346 (2025)Cite this article

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Abstract

The electrochemical conversion of CO2 into acetaldehyde offers a sustainable and green alternative to the Wacker process. However, current electrocatalysts cannot effectively compete with heterogeneous processes owing to their limited selectivity towards acetaldehyde, resulting in low energy efficiencies. Here we report a theory-guided synthesis of a series of Cu-cluster catalysts (~1.6 nm) immobilized on various heteroatom-doped carbonaceous supports, produced via spark ablation of Cu electrodes (2.6 μg h−1 production rate, 6 Wh energy consumption). These catalysts achieve acetaldehyde selectivity of up to 92% at only 600 mV from the equilibrium potential. In addition, the catalysts exhibit exceptional catalytic stability during a rigorous 30 h stress test involving three repeated start–stop cycles. In situ X-ray absorption spectroscopy reveals that the initial oxide clusters were completely reduced under cathodic potential and maintained their metallic nature even after exposure to air, explaining the stable performance of the catalyst. First-principles simulations further elucidate a possible mechanism of CO2 conversion to acetaldehyde.

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Fig. 1: Computational catalyst screening.
Fig. 2: Scalable and atomically precise catalyst synthesis via spark ablation.
Fig. 3: Advanced characterization of the as-synthesized Cu(–Ag) oxide clusters immobilized on heteroatom-doped carbonaceous support.
Fig. 4: Electrocatalytic screening for CO2 reduction to acetaldehyde.
Fig. 5: In situ activation of the precatalyst.
Fig. 6: Mechanistic insight in the facile conversion of CO2 to acetaldehyde on Cu clusters.

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Data availability

All data are available in the article and its Supplementary Information. Source data are provided with this paper.

Code availability

DFT-simulated atomic structures and scripts necessary for reproducing the simulated results have been made freely available at https://nano.ku.dk/english/research/theoretical-electrocatalysis/katladb/co2-to-acetaldehyde/.

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Acknowledgements

This research was supported by Swiss National Science Foundation (Ambizione Project PZ00P2_179989, W.L.). The in situ XAS cell used in this work was developed in the framework of the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement number 955650 (O.V.S. and J.H.). We acknowledge the financial support from China Scholarship Council (grant number 201506060156, M.L). We acknowledge support from the Danish National Research Foundation Center for High Entropy Alloy Catalysis (CHEAC) DNRF-149 (J.K.P.). We acknowledge the financial support by the Swiss National Foundation (project 184817, A.A.) and the Energy Systems Integration (ESI) Platform at the Paul Scherrer Institute. We also thank C. Ludwig of the Bioenergy and Catalysis Laboratory (LBK), Energy and Environment Research Division (ENE), Paul Scherrer Institute (PSI) and the School of Architecture, Civil, and Environmental Engineering (ENAC IIE GR-LUD), École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland for the lively discussions. L. Menin and N. Gasilova of the Mass Spectrometry and Elemental Analysis Platform (MSEAP), Institute of Chemical Sciences and Engineering (ISIC), Basic Science Faculty (SB), École Polytechnique Fédérale de Lausanne (EPFL) Valais/Wallis, Energypolis, Sion, Switzerland, are acknowledged for their facilitation of the inductively coupled plasma mass spectrometry measurements. B. Boshuizen of Faculty of Applied Sciences Technical University of Delft, Delft, the Netherlands, is acknowledged for his XPS measurement of Cu(–Ag) oxide catalysts after production. A. Bornet of the Nuclear Magnetic Resonance Platform, Institute of Chemical Sciences and Engineering (ISIC), Basic Science Faculty (SB), École polytechnique fédérale de Lausanne (EPFL), Switzerland, is acknowledged for his assistance with H-NMR experiments. Y. Ko, Y. Wang and L. Zhong of the Laboratory of Materials for Renewable Energy (LMER), Institute of Chemical Sciences and Engineering (ISIC), Basic Science Faculty (SB), École polytechnique fédérale de Lausanne (EPFL) Valais/Wallis, Energypolis, Sion, Switzerland, are acknowledged for their assistance with the GO synthesis protocol, their assistance with the Brunauer-Emmett-Teller (BET) measurements and the design of Fig. 2 and contribution to XPS measurements, respectively. We acknowledge A. H. Clark of the Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland, for his support during the in situ synchrotron experiment. Finally, we acknowledge J. Rossmeisl of the Center for High Entropy Alloy Catalysis, Department of Chemistry, University of Copenhagen, Copenhagen, Denmark, for initial discussions on the design of the DFT simulations. Graphical abstract adapted with permission from ref. 28, American Chemical Society.

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Authors and Affiliations

  1. Laboratory of Materials for Renewable Energy, Institute of Chemical Sciences and Engineering, Basic Science Faculty, École polytechnique fédérale de Lausanne Valais/Wallis, Energypolis, Sion, Switzerland

    Cedric David Koolen, Jie Zhang, Mo Li, Zohreh Akbari, Yasemen Kuddusi & Andreas Zuettel

  2. Empa Materials Science and Technology, Dübendorf, Switzerland

    Cedric David Koolen, Zohreh Akbari, Yasemen Kuddusi & Andreas Zuettel

  3. Center for High Entropy Alloy Catalysis, Department of Chemistry, University of Copenhagen, Copenhagen, Denmark

    Jack Kirk Pedersen

  4. VSPARTICLE B.V., Delft, the Netherlands

    Bernardus Zijlstra, Tobias V. Pfeiffer, Wilbert Vrijburg & Andreas Schmidt-Ott

  5. Paul Scherrer Institute, PSI Center for Energy and Environmental Sciences, Villigen PSI, Villigen, Switzerland

    Maximilian Winzely, Ayush Agarwal, Juan Herranz & Olga V. Safonova

  6. Environmental Engineering Institute, School of Architecture, Civil and Environmental Engineering, École Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

    Ayush Agarwal

  7. Faculty of Applied Sciences, Technical University of Delft, Delft, the Netherlands

    Andreas Schmidt-Ott

  8. School of Environmental and Chemical Engineering, Shanghai University, Shanghai, China

    Wen Luo

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  1. Cedric David Koolen
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Contributions

C.D.K. and J.K.P. conceptualized the project. C.D.K., W.L. and A.Z. supervised the project. C.D.K. and B.Z. developed the cluster production and associated characterization with contributions from T.V.P., W.V. and A.S.-O. C.D.K. developed the catalyst synthesis, characterization and related data processing. C.D.K. performed and interpretated the electrochemical tests with contributions from J.Z. W.L. and M.L. performed the XPS analysis and data treatment with contributions from Y.K. C.D.K., M.W., A.A., J.Z., J.H. and O.V.S. designed the in situ XAS experiments. M.W. and J.H. provided the spectroelectrochemical cell. C.D.K., M.W., A.A., Z.A. and Y.K. performed the in situ XAS experiment. O.V.S. performed the ex situ XAS experiments. C.D.K. performed the data treatment of XAS experiments with contributions from M.W. and O.V.S. J.K.P performed all DFT simulations. C.D.K., J.K.P. and W.L. co-wrote the paper. All the authors discussed the results and revised the paper. Questions regarding the synthesis, catalysis and characterization should be directed to C.D.K. All questions related to the DFT simulation should be directed to J.K.P.

Corresponding authors

Correspondence to Cedric David Koolen, Jack Kirk Pedersen or Wen Luo.

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Competing interests

This technology is part of a patent application (PCT/EP2024/058885). C.D.K. has become an advisor of VSParticle B.V. as a direct result of this collaboration. T.V.P. and A.S.-O. are founders of VSParticle B.V. B.Z. and W.V. are former employees of VSParticle B.V. The other authors declare no competing interests.

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Nature Synthesis thanks Yan Zhao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Thomas West, in collaboration with the Nature Synthesis team.

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Extended data

Extended Data Fig. 1 Description of the spark ablation and electrostatic deposition experimental set-up, operation, and electrical components.

(a) Faraday cup used to collect either negatively or positively charged particles from the aerosol. The measured current (via an electrometer) allows to determine the number of ions hitting the cup per unit of time giving a measure of the ablation rate (cluster production rate)77,78. (b) Deposition chamber allowing for a filter deposition in which the entire aerosol flow is passed through a substrate as well as an electrostatic deposition method in which a bias is applied to a substrate and as such only particles of opposite polarity are adhered to it79. (c) Aerosol exhaust. (d) Positive electrode (grounded). (e) Spark chamber. (f) Carrier gas (Ar) flow inlet. Direction of flow is from (E) to (B). (g) Negative electrode. (h) Pin-to-hole configuration of the electrode set-up of the spark ablator showing two Cu electrodes80. Exchanging the pin or negative electrode for Ag allows for the production of bimetallic clusters81,82,83,84. (i) Picture of the spark in operation. (j) Resistance-inductance-capacitance (RLC) electrical circuit, in which I denote the power supply. C denote(s) the capacitor, L denotes the inductor needed to store potential energy via the magnetic field needed for the oscillatory nature of the spark85. The spark is indicated by the damped exponential with a ~100 ns time constant of the oscillation of the spark between the grounded and negative electrode.

Supplementary information

Supplementary Information

Supplementary Figs. 1–40, Notes 1–9, Tables 1–14 and References 1–26.

Source data

Source Data Fig. 3

Statistical source data.

Source Data Fig. 4

Statistical source data.

Source Data Fig. 5

Statistical source data.

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Koolen, C.D., Pedersen, J.K., Zijlstra, B. et al. Scalable synthesis of Cu-cluster catalysts via spark ablation for the electrochemical conversion of CO2 to acetaldehyde. Nat. Synth 4, 336–346 (2025). https://doi.org/10.1038/s44160-024-00705-3

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