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Interfacial electronic effects control the reaction selectivity of platinum catalysts

Nature Materials volume 15, pages 564–569 (2016)Cite this article

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Abstract

Tuning the electronic structure of heterogeneous metal catalysts has emerged as an effective strategy to optimize their catalytic activities. By preparing ethylenediamine-coated ultrathin platinum nanowires as a model catalyst, here we demonstrate an interfacial electronic effect induced by simple organic modifications to control the selectivity of metal nanocatalysts during catalytic hydrogenation. This we apply to produce thermodynamically unfavourable but industrially important compounds, with ultrathin platinum nanowires exhibiting an unexpectedly high selectivity for the production of N-hydroxylanilines, through the partial hydrogenation of nitroaromatics. Mechanistic studies reveal that the electron donation from ethylenediamine makes the surface of platinum nanowires highly electron rich. During catalysis, such an interfacial electronic effect makes the catalytic surface favour the adsorption of electron-deficient reactants over electron-rich substrates (that is, N-hydroxylanilines), thus preventing full hydrogenation. More importantly, this interfacial electronic effect, achieved through simple organic modifications, may now be used for the optimization of commercial platinum catalysts.

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Figure 1: Structure analysis of the ultrathin Pt NWs.
Figure 2: Catalytic performance of EDA-Pt NWs.
Figure 3: The surface electronic effect induced by EDA.
Figure 4: Mechanism of catalytic selectivity of EDA-Pt NWs.

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Acknowledgements

We thank the MOST of China (2015CB932303), the NSFC (21420102001, 21131005, 21390390, 21333008, 21373167, 21133004), IRT_14R31, and the NFFTBS (J1210014) for the financial support. We thank Y. P. Zheng for help with XPS measurements, S. Q. Wei for preliminary XAS tests, Y. Ding and Z. L. Wang for preliminary HRTEM measurements. We also thank L. S. Zheng, Z. Q. Tian, L. W. Ye., M. S. Chen, B. Ren, J. F. Li, P. Zhang, Y. Zhao, J. Yang and P. N. Duchesne for helpful discussions.

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Author notes

  1. Guangxu Chen and Chaofa Xu: These authors contributed equally to this work.

Authors and Affiliations

  1. Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, Xiamen 361005, China

    Guangxu Chen, Chaofa Xu, Xiaoqing Huang, Jinyu Ye, Binghui Wu, Huayan Yang, Zipeng Zhao, Zhiyou Zhou, Gang Fu & Nanfeng Zheng

  2. National Engineering Laboratory for Green Chemical Productions of Alcohols–Ethers–Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

    Guangxu Chen, Chaofa Xu, Xiaoqing Huang, Binghui Wu, Huayan Yang, Zipeng Zhao, Gang Fu & Nanfeng Zheng

  3. Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

    Lin Gu

  4. State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

    Gang Li & Zichao Tang

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Contributions

N.Z. conceived the research project. G.C., C.X., X.H., Z.Z. and B.W. designed and synthesized the nanomaterials and carried out the catalysis experiments. G.F. carried out the model construction and DFT calculations. G.L. and Z.T. performed the TPD-MS experiments. J.Y. and Z.Z. carried out the in situ FTIR spectroscopy experiments. L.G. performed the HRTEM measurements. H.Y. performed the single-crystal analysis. All the authors contributed to the data analysis and drafted the manuscript.

Corresponding authors

Correspondence to Gang Fu or Nanfeng Zheng.

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Chen, G., Xu, C., Huang, X. et al. Interfacial electronic effects control the reaction selectivity of platinum catalysts. Nature Mater 15, 564–569 (2016). https://doi.org/10.1038/nmat4555

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