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Selective CO2 electrocatalysis at the pseudocapacitive nanoparticle/ordered-ligand interlayer

Nature Energy volume 5, pages 1032–1042 (2020)Cite this article

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Abstract

Enzymes feature the concerted operation of multiple components around an active site, leading to exquisite catalytic specificity. Realizing such configurations on synthetic catalyst surfaces remains elusive. Here, we report a nanoparticle/ordered-ligand interlayer that contains a multi-component catalytic pocket for high-specificity CO2 electrocatalysis. The nanoparticle/ordered-ligand interlayer comprises a metal nanoparticle surface and a detached layer of ligands in its vicinity. This interlayer possesses unique pseudocapacitive characteristics where desolvated cations are intercalated, creating an active-site configuration that enhances catalytic turnover by two orders and one order of magnitude against a pristine metal surface and nanoparticle with tethered ligands, respectively. The nanoparticle/ordered-ligand interlayer is demonstrated across several metals with up to 99% CO selectivity at marginal overpotentials and onset overpotentials of as low as 27 mV, in aqueous conditions. Furthermore, in a gas-diffusion environment with neutral media, the nanoparticle/ordered-ligand interlayer achieves nearly unit CO selectivity at high current densities (98.1% at 400 mA cm−2).

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Fig. 1: Formation of a NOLI and a metal-NOLI catalyst for selective electrocatalysis.
Fig. 2: NOLI formed by the collective dissociation of ligands from an assembly of NPs.
Fig. 3: Stable ligand layer of the NOLI and its reversible physisorption.
Fig. 4: Pseudocapacitive behaviour of the NOLI.
Fig. 5: Cation association at the NOLI.
Fig. 6: Catalytic mechanism of the NOLI.
Fig. 7: Au-NOLI and Pd-NOLI for selective CO2 electrocatalysis in an H-cell configuration, and catalytic performance of Ag-NOLI in a GDE configuration.

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The data supporting the findings of this study are available within the paper and Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, of the US Department of Energy under contract no. DE-AC02-05CH11231, FWP CH030201 (Catalysis Research Program). F.Z. and L.-W.W. were supported by Joint Center for Artificial Photosynthesis, a US Department of Energy Energy Innovation Hub, supported through the Office of Science of the US Department of Energy under award no. DE-SC0004993. We used resources of the National Energy Research Scientific Computing Center (NERSC) and resources from National Renewable Energy Laboratory (NREL). H.F. was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical, Geological and Biosciences of the US Department of Energy under contract no. DE-AC02-05CH11231, FWP KC0304030 (Solar Photochemistry Research Program). Work at the Molecular Foundry was supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. This research used resources of the Advanced Light Source, which is a US Department of Energy Office of Science User Facility, under contract no. DE-AC02-05CH11231. We thank S. Fakra for assistance with X-ray absorption spectroscopy experiments at Beamline 10.3.2 at the Advanced Light Source. We thank H. Celik and the University of California at Berkeley’s NMR facility in the College of Chemistry for spectroscopic assistance. Instruments in the NMR facility in the College of Chemistry are supported in part by the National Institutes of Health under grant no. S10OD024998. This work made use of the facility at the Lawrence Berkeley National Laboratory Catalysis Laboratory, which is supported by the US Department of Energy, Office of Science, Basic Energy Sciences, under contract no. DE-AC02-05CH11231. Inductively coupled plasma optical emission spectrometry was supported by the Microanalytical Facility, College of Chemistry, University of California, Berkeley. We also thank T. Lin and J. Chan for experimental assistance. D.K. and S.Y. acknowledge support from Samsung Scholarship.

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Author notes

  1. These authors contributed equally: Dohyung Kim, Sunmoon Yu.

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of California, Berkeley, CA, USA

    Dohyung Kim, Sunmoon Yu & Peidong Yang

  2. Department of Chemistry, University of California, Berkeley, CA, USA

    Dohyung Kim, Inwhan Roh, Yifan Li, Sheena Louisia, Gabor A. Somorjai & Peidong Yang

  3. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Dohyung Kim, Sunmoon Yu, Inwhan Roh, Yifan Li, Sheena Louisia, Zhiyuan Qi & Peidong Yang

  4. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Fan Zheng, Gabor A. Somorjai & Lin-Wang Wang

  5. Joint Center for Artificial Photosynthesis, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Fan Zheng & Lin-Wang Wang

  6. Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Heinz Frei

  7. Kavli Energy NanoScience Institute, Berkeley, CA, USA

    Peidong Yang

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Contributions

D.K. and S.Y. designed and performed the experiments, and analysed data with assistance from I.R., Y.L. and S.L.; F.Z. conducted MD simulation under the supervision of L.-W.W.; H.F. assisted with the infrared spectroscopy measurements. Z.Q. conducted SFG spectroscopy measurements under the guidance of G.A.S.; P.Y. supervised the project and experimental design. All authors wrote the manuscript.

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Correspondence to Peidong Yang.

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Supplementary Figs. 1–54, Note 1 and Tables 1–8.

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Kim, D., Yu, S., Zheng, F. et al. Selective CO2 electrocatalysis at the pseudocapacitive nanoparticle/ordered-ligand interlayer. Nat Energy 5, 1032–1042 (2020). https://doi.org/10.1038/s41560-020-00730-4

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