ABSTRACT 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

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REAL-SPACE IMAGING OF A PHENYL GROUP MIGRATION REACTION ON METAL SURFACES Article Open access 21 February 2023 SMALL MOLECULE BINDING TO SURFACE-SUPPORTED SINGLE-SITE TRANSITION-METAL

REACTION CENTRES Article Open access 01 December 2022 SINGLE HYDROGEN ATOM MANIPULATION FOR REVERSIBLE DEPROTONATION OF WATER ON A RUTILE TIO2 (110) SURFACE Article Open access 19 January

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. CODE AVAILABILITY 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

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method for finding saddle points and minimum energy paths. _J. Chem. Phys._ 113, 9901 (2000). CAS  Google Scholar  Download references ACKNOWLEDGEMENTS 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 INFORMATION AUTHORS 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 Authors * Hao Yin View author publications You can also search for this author inPubMed Google Scholar * Li-Qing Zheng View author

publications You can also search for this author inPubMed Google Scholar * Wei Fang View author publications You can also search for this author inPubMed Google Scholar * Yin-Hung Lai View

author publications You can also search for this author inPubMed Google Scholar * Nikolaus Porenta View author publications You can also search for this author inPubMed Google Scholar *

Guillaume Goubert View author publications You can also search for this author inPubMed Google Scholar * Hua Zhang View author publications You can also search for this author inPubMed 

Google Scholar * Hai-Sheng Su View author publications You can also search for this author inPubMed Google Scholar * Bin Ren View author publications You can also search for this author

inPubMed Google Scholar * Jeremy O. Richardson View author publications You can also search for this author inPubMed Google Scholar * Jian-Feng Li View author publications You can also

search for this author inPubMed Google Scholar * Renato Zenobi View author publications You can also search for this author inPubMed Google Scholar CONTRIBUTIONS 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. ETHICS

DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. ADDITIONAL INFORMATION PUBLISHER’S NOTE Springer Nature remains neutral with regard to jurisdictional claims in

published maps and institutional affiliations. SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Supplementary Figs. 1–25, discussion and Tables 1 & 2. SUPPLEMENTARY DATA 1 Cartesian

coordinates (Å) for the optimized geometries in DFT calculations. SOURCE DATA SOURCE DATA FIG. 1 Cyclic voltammetry data and Raman signals for Fig. 1. SOURCE DATA FIG. 2 Raw spectrum data

without background subtraction for Fig. 2. SOURCE DATA FIG. 3 Statistical source data for Fig. 3. SOURCE DATA FIG. 4 Statistical source data for Fig. 4. SOURCE DATA FIG. 5 Statistical source

data for Fig. 5. SOURCE DATA FIG. 6 Statistical source data for Fig. 6. RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE 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 Download citation * Received: 21 January 2020 * Accepted: 06 August 2020 * Published: 21 September 2020 * Issue Date: October 2020 * DOI:

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