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Bimetallic monolayer catalyst breaks the activity–selectivity trade-off on metal particle size for efficient chemoselective hydrogenations

Nature Catalysis volume 4, pages 840–849 (2021)Cite this article

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Abstract

Particle size governs the geometric and electronic structure of metal nanoparticles (NPs), shaping their catalytic performance. However, size-dependent entanglement in the geometric and electronic structures often leads to a trade-off between activity and selectivity, limiting the optimization of the overall catalytic performance. Here we show that precisely controlled deposition of a platinum monolayer on large gold NPs breaks the activity–selectivity trade-off on particle size in platinum-catalysed chemoselective hydrogenation of halonitrobenzenes, resulting in a remarkable activity, along with a 99% selectivity for haloanilines under mild conditions. The high activity results from upshift of the platinum 5d-band centre through platinum lattice expansion and ligand effect, whereas the high selectivity is caused by exposing more terrace sites on large particles. The geometric and electronic properties of bimetallic monolayer materials, distinct from monometallic NPs and alloys, constitute a promising platform for the rational design of metal catalysts with superior performance in hydrogenation reactions.

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Fig. 1: Catalytic performance of Pt/SiO2 catalysts in the hydrogenation of HNBs.
Fig. 2: Calculated parameters of hydrogenation of p-CNB on platinum surfaces.
Fig. 3: Morphology of Au@Pt core–shell catalysts.
Fig. 4: Electronic properties of platinum monometallic and Au@Pt core–shell catalysts.
Fig. 5: Comparison of catalytic performance of platinum-based catalysts in chemoselective hydrogenation of p-CNB.

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The data generated during this study are included in this article (and its Supplementary Information files) or can be obtained from the authors upon reasonable request.

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Acknowledgements

J.L. acknowledges support from the National Natural Science Foundation of China (22025205, 21673215), the Dalian National Laboratory for Clean Energy (DNL) Cooperation Fund (DNL201907), the Fundamental Research Funds for the Central Universities (WK2060030029), and Users with Excellence Program of Hefei Science Center CAS (2019HSC-UE016). W.-X.L. acknowledges the National Key R&D Program of China (2018YFA0208603), the National Natural Science Foundation of China (91945302), the Dalian National Laboratory for Clean Energy (DNL) Cooperation Fund (DNL201920), the Chinese Academy of Sciences (QYZDJ-SSW-SLH054) and K.C. Wong Education (GJTD-2020-15). Y.L. acknowledges support from the Youth Innovation Promotion Association of the CAS (2020458). Y.Y. acknowledges support from the National Natural Science Foundation of China (22072092, 92045301). S.W. acknowledges the National Key R&D Program of China (2017YFA0402800). The authors all gratefully thank the BL14W1 beamline at the Shanghai Synchrotron Radiation Facility (SSRF) and Supercomputing Center of University of Science and Technology of China and National Supercomputing Center in Zhengzhou.

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  1. These authors contributed equally Q. Guan, C. Zhu.

Authors and Affiliations

  1. School of Chemistry and Materials Science, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, University of Science and Technology of China, Hefei, China

    Qiaoqiao Guan, Chuwei Zhu, Hancheng Yu, Xiaohui Zhang, Xinyu Liu, Mengkai Zhang, Wei-Xue Li & Junling Lu

  2. Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, China

    Yue Lin, Lina Cao, Hengwei Wang, Wei-Xue Li & Junling Lu

  3. School of Physical Science and Technology, ShanghaiTech University, Shanghai, China

    Evgeny I. Vovk, Xiaohong Zhou & Yong Yang

  4. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, China

    Shiqiang Wei

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Contributions

J.L. designed the experiments and W.-X.L. designed the DFT calculations. Q.G. synthesized and characterized the catalysts and evaluated the catalytic performance. C.Z. did the DFT calculations. Y.L. did the HAADF-STEM measurements. E.I.V., X.Z. and Y.Y. did the XPS measurements. H.Y., L.C., H.W., X.Z., X.L. and M.Z. assisted the catalyst characterization and catalytic performance evolution. S.W. performed the XAFS measurements. J.L. and W.-X.L. co-wrote the manuscript, and all the authors contributed to the overall scientific interpretation and edited the manuscript.

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Correspondence to Wei-Xue Li or Junling Lu.

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Peer review Information Nature Catalysis thanks Meenakshisundaram Sankar and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–36, Tables 1–9 and References.

Supplementary Data 1

A zipped file containing the source data of Supplementary Figs. 1–35 and DFT-calculated coordination parameters. Therein, the file Supplementary_Figures_1-7,10,14,21,23,27-35 corresponds to the original data in the supplementary figures, while the file XYZ_coordination_parameters.docx contains the atomic coordinates of the optimized DFT models used in this article.

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Guan, Q., Zhu, C., Lin, Y. et al. Bimetallic monolayer catalyst breaks the activity–selectivity trade-off on metal particle size for efficient chemoselective hydrogenations. Nat Catal 4, 840–849 (2021). https://doi.org/10.1038/s41929-021-00679-x

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