Nanometre-scale spectroscopic visualization of catalytic sites during a hydrogenation reaction on a Pd/Au bimetallic catalyst

Article Published: 21 September 2020 Nanometre-scale spectroscopic visualization of catalytic sites during a hydrogenation reaction on a Pd/Au bimetallic catalyst Hao Yin  ORCID:

orcid.org/0000-0002-9469-83011,2, Li-Qing Zheng  ORCID: orcid.org/0000-0001-7848-69851, Wei Fang  ORCID: orcid.org/0000-0001-9584-84661, Yin-Hung Lai1, Nikolaus Porenta1, Guillaume Goubert1,

Hua Zhang2, Hai-Sheng Su2, Bin Ren  ORCID: orcid.org/0000-0002-9821-58642, Jeremy O. Richardson  ORCID: orcid.org/0000-0002-9429-151X1, Jian-Feng Li  ORCID: orcid.org/0000-0003-1598-68562 &

…Renato Zenobi  ORCID: orcid.org/0000-0001-5211-43581 Show authors Nature Catalysis volume 3, pages 834–842 (2020)Cite this article

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Understanding the mechanism of catalytic hydrogenation at the local environment requires chemical and topographic information involving catalytic sites, active hydrogen species, and their

spatial distribution. Here we used tip-enhanced Raman spectroscopy (TERS) to study the catalytic hydrogenation of chloronitrobenzenethiol on a well-defined Pd(submonolayer)/Au(111)

bimetallic catalyst (\(p_{\rm{H}_{2}}\) = 1.5 bar, 298 K), where the surface topography and chemical fingerprint information were simultaneously mapped with nanoscale resolution (~10 nm).

TERS imaging of the surface after catalytic hydrogenation confirms that the reaction occurs beyond the location of Pd sites. The results demonstrate that hydrogen spillover accelerates

hydrogenation at Au sites as far as 20 nm from the bimetallic Pd/Au boundary. Density functional theory was used to elucidate the thermodynamics of interfacial hydrogen transfers. We

demonstrate TERS to be a powerful analytical tool that provides a unique approach to spatially investigate the local structure–reactivity relationship in catalysis.

Access through your institution Buy or subscribe This is a preview of subscription content, access via your institution

options: Log in Learn about institutional subscriptions Read our FAQs Contact customer support Fig. 1: TERS studies of monometallic and bimetallic model catalysts.Fig. 2: TERS line scan

results.Fig. 3: TERS 2D maps.Fig. 4: TERS maps revealing hydrogen spillover.Fig. 5: Hydrogen spillover region identification.Fig. 6: DFT calculations. Similar content being viewed by others

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2021 Data availability

The original data used in this publication are made available in a curated data archive at ETH Zurich (https://www.researchcollection.ethz.ch) under https://doi.org/10.3929/ethz-b-000423837,

or are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

The MATLAB codes used for processing the data are made available in a curated data archive at ETH Zurich (https://www.researchcollection.ethz.ch) under

https://doi.org/10.3929/ethz-b-000423837, or are available from the corresponding authors upon reasonable request.

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This work was supported financially by the European Research Council program (grant number 741431—2DNanoSpec), the Natural Science Foundation of China (grant numbers 21925404, 21775127 and

21703181), the Fundamental Research Funds for the Central Universities (20720190044) and MOST (2019YFA0705402). L.-Q.Z. was financially supported by the Chinese Scholarship Council for a PhD

student fellowship. H.Y. was financially supported by the Sino‐Swiss Science and Technology Cooperation program (grant number EG22‐122016). W.F. and J.O.R. are supported by the Swiss

National Science Foundation (project number 175696.) We thank A. Rossi (ETH Zurich) and G. Cossu (ETH Zurich) for help with the XPS measurements. DFT computations were supported by the

High-Performance Computing Team at ETH Zurich. H.Y. and L.-Q.Z. also thank A. Begley, J.B. Metternich, J. Szczerbińsky and J.A. van Bokhoven (all from ETH Zurich) for insightful discussions.

H.Y. thanks W.-Q. Li (Xiamen University) for the coverage measurements.

Author informationAuthors and Affiliations Department of Chemistry and Applied Biosciences, ETH Zurich, Zurich, Switzerland

Hao Yin, Li-Qing Zheng, Wei Fang, Yin-Hung Lai, Nikolaus Porenta, Guillaume Goubert, Jeremy O. Richardson & Renato Zenobi

State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering,

College of Energy, College of Materials, Xiamen University, Xiamen, China

Hao Yin, Hua Zhang, Hai-Sheng Su, Bin Ren & Jian-Feng Li

AuthorsHao YinView author publications You can also search for this author inPubMed Google Scholar

Li-Qing ZhengView author publications You can also search for this author inPubMed Google Scholar

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R.Z. and J.-F.L. supervised the project. L.-Q.Z. conceived of the ideas. L.-Q.Z. and H.Y. designed the experiments. H.Y., L.-Q.Z. and N.P. performed the experiments. W.F. and J.O.R.

performed the DFT calculations. Y.-H.L. and L.-Q.Z. performed the TPD-MS experiments. G.G., H.-S.S. and B.R. contributed to the electrochemistry. H.Y., L.-Q.Z. and W.F. wrote the manuscript

with the help of G.G. and H.Z. All authors discussed the results and commented on the manuscript.

Corresponding authors Correspondence to Li-Qing Zheng, Jeremy O. Richardson, Jian-Feng Li or Renato Zenobi.

The authors declare no competing interests.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Figs. 1–25, discussion and Tables 1 & 2.

Cartesian coordinates (Å) for the optimized geometries in DFT calculations.

Cyclic voltammetry data and Raman signals for Fig. 1.

Raw spectrum data without background subtraction for Fig. 2.

Statistical source data for Fig. 3.

Statistical source data for Fig. 4.

Statistical source data for Fig. 5.

Statistical source data for Fig. 6.

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About this articleCite this article Yin, H., Zheng, LQ., Fang, W. et al. Nanometre-scale spectroscopic visualization of catalytic sites during a hydrogenation reaction on a Pd/Au bimetallic

catalyst. Nat Catal 3, 834–842 (2020). https://doi.org/10.1038/s41929-020-00511-y

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Received: 21 January 2020

Accepted: 06 August 2020

Published: 21 September 2020

Issue Date: October 2020

DOI: https://doi.org/10.1038/s41929-020-00511-y

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