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Microstructural origin of locally enhanced CO2 electroreduction activity on gold

Nature Materials volume 20, pages 1000–1006 (2021)Cite this article

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Abstract

Understanding how the bulk structure of a material affects catalysis on its surface is critical to the development of actionable catalyst design principles. Bulk defects have been shown to affect electrocatalytic materials that are important for energy conversion systems, but the structural origins of these effects have not been fully elucidated. Here we use a combination of high-resolution scanning electrochemical cell microscopy and electron backscatter diffraction to visualize the potential-dependent electrocatalytic carbon dioxide \(({\mathrm{C}}{\mathrm{O}}_{2})\) electroreduction and hydrogen \(({{\mathrm{H}}_{2}})\) evolution activity on Au electrodes and probe the effects of bulk defects. Comparing colocated activity maps and videos to the underlying microstructure and lattice deformation supports a model in which CO2 electroreduction is selectively enhanced by surface-terminating dislocations, which can accumulate at grain boundaries and slip bands. Our results suggest that the deliberate introduction of dislocations into materials is a promising strategy for improving catalytic properties.

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Fig. 1: Experimental approach for investigating microstructure effects in electrocatalysis at Au electrodes.
Fig. 2: Probing microstructure dependence of H2 evolution activity.
Fig. 3: Probing microstructure dependence of CO2 electroreduction activity.
Fig. 4: HR-EBSD mapping of area within Sample A that was scanned with SECCM, shown in Fig. 3.
Fig. 5: EBSD and SECCM mapping of a highly deformed region surrounding a 42° GB in Sample B.

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Data availability

The authors declare that all data supporting the findings of this study are included within the paper and its Supplementary Information files. Source data are available from the corresponding authors upon reasonable request.

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Acknowledgements

Work at Stanford was supported by the National Science Foundation (CHE-1855950). R.G.M. gratefully acknowledges Stanford University for a DARE fellowship and J.A.R. gratefully acknowledges a Stanford Graduate Fellowship. M.K. and P.R.U. are grateful to the Warwick–Monash Accelerator Fund for support. M.K. also acknowledges support from the Leverhulme Trust for an Early Career Fellowship. I.J.M. and P.R.U. are supported by Engineering and Physical Sciences Research Council Programme Grant EP/R018820/1. P.R.U. thanks the Royal Society for a Wolfson Research Merit Award. O.J.W. acknowledges support from the University of Warwick Chancellor’s International Scholarship. Parts of this work were performed at the Stanford Nano Shared Facilities, which is supported by the National Science Foundation under award ECCS-1542152.

Author information

Author notes

  1. These authors contributed equally: Ruperto G. Mariano, Minkyung Kang.

Authors and Affiliations

  1. Department of Chemistry, Stanford University, Stanford, CA, USA

    Ruperto G. Mariano, Joshua A. Rabinowitz & Matthew W. Kanan

  2. Department of Chemistry, University of Warwick, Coventry, UK

    Minkyung Kang, Oluwasegun J. Wahab, Ian J. McPherson & Patrick R. Unwin

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  1. Ruperto G. Mariano
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Contributions

R.G.M., M.K., P.R.U. and M.W.K. conceived and designed the study. R.G.M., M.K. and O.J.W. performed SECCM experiments. O.J.W. prepared Au samples for SECCM imaging. R.G.M. and J.A.R. performed gas diffusion electrode electrolysis studies. R.G.M., M.K. and O.J.W. performed SEM/EBSD imaging of the samples, and R.G.M. performed HR-EBSD measurements and analysis. I.J.M. and P.R.U. designed the finite element method calculations, and I.J.M. built the COMSOL model. R.G.M., M.K. and M.W.K. wrote the initial draft of the paper, and all authors contributed to the final version.

Corresponding authors

Correspondence to Patrick R. Unwin or Matthew W. Kanan.

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The authors declare no competing interests.

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Peer review information Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–13, Tables 1–5, Notes 1 and 2, captions for Videos 1–5 and references.

Supplementary Video 1

Spatially resolved electrochemical video (707 pixels over a 49 μm × 7.7 μm scan area, 220 image frames) obtained with the voltammetric SECCM protocol, visualizing activity of H2 evolution on Sample A.

Supplementary Video 2

Spatially resolved electrochemical video (1,140 pixels over a 30 μm × 9.5 μm scan area, 220 image frames) obtained with the voltammetric SECCM protocol, visualizing activity of CO2 electroreduction on Sample A.

Supplementary Video 3

Spatially resolved electrochemical video (369 pixels over a 20.5 μm × 4.5 μm scan area, 220 image frames) obtained with the voltammetric SECCM protocol, visualizing activity of H2 evolution on Sample A.

Supplementary Video 4

Spatially resolved electrochemical video (1,281 pixels over a 30.5 μm × 10.5 μm scan area, 220 image frames) obtained with the voltammetric SECCM protocol, visualizing activity of CO2 electroreduction on Sample A.

Supplementary Video 5

Spatially resolved electrochemical video (756 pixels over a 13.5 μm × 14 μm scan area, 220 image frames) obtained with the voltammetric SECCM protocol, visualizing activity of CO2 electroreduction on Sample B.

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Mariano, R.G., Kang, M., Wahab, O.J. et al. Microstructural origin of locally enhanced CO2 electroreduction activity on gold. Nat. Mater. 20, 1000–1006 (2021). https://doi.org/10.1038/s41563-021-00958-9

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