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Synergetic interaction between neighbouring platinum monomers in CO2 hydrogenation

Nature Nanotechnologyvolume 13pages411417 (2018) | Download Citation


Exploring the interaction between two neighbouring monomers has great potential to significantly raise the performance and deepen the mechanistic understanding of heterogeneous catalysis. Herein, we demonstrate that the synergetic interaction between neighbouring Pt monomers on MoS2 greatly enhanced the CO2 hydrogenation catalytic activity and reduced the activation energy relative to isolated monomers. Neighbouring Pt monomers were achieved by increasing the Pt mass loading up to 7.5% while maintaining the atomic dispersion of Pt. Mechanistic studies reveal that neighbouring Pt monomers not only worked in synergy to vary the reaction barrier, but also underwent distinct reaction paths compared with isolated monomers. Isolated Pt monomers favour the conversion of CO2 into methanol without the formation of formic acid, whereas CO2 is hydrogenated stepwise into formic acid and methanol for neighbouring Pt monomers. The discovery of the synergetic interaction between neighbouring monomers may create a new path for manipulating catalytic properties.

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  1. 1.

    Tyo, E. C. & Vajda, S. Catalysis by clusters with precise numbers of atoms. Nat. Nanotech. 10, 577–588 (2015).

  2. 2.

    Grundner, S. et al. Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol. Nat. Commun. 6, 7546 (2015).

  3. 3.

    Serna, P. & Gates, B. C. Zeolite-supported rhodium complexes and clusters: switching catalytic selectivity by controlling structures of essentially molecular species. J. Am. Chem. Soc. 133, 4714–4717 (2011).

  4. 4.

    Ghosh, T. K. & Nair, N. N. Alumina-supported Rh, Rh2, and RhI(CO) as catalysts for hydrogen evolution from water. Surf. Sci. 632, 20–27 (2015).

  5. 5.

    Chen, M., Kumar, D., Yi, C. W. & Goodman, D. W. The promotional effect of gold in catalysis by palladium–gold. Science 310, 291–293 (2005).

  6. 6.

    Yardimci, D., Serna, P. & Gates, B. C. Surface-mediated synthesis of dimeric rhodium catalysts on MgO: tracking changes in the nuclearity and ligand environment of the catalytically active sites by X-ray absorption and infrared spectroscopies. Chem. Eur. J. 19, 1235–1245 (2013).

  7. 7.

    Wang, L. et al. Supported rhodium catalysts for ammonia-borane hydrolysis: dependence of the catalytic activity on the highest occupied state of the single rhodium atoms. Angew. Chem. Int. Ed. 56, 4712–4718 (2017).

  8. 8.

    Jones, J. et al. Thermally stable single-atom platinum-on-ceria catalysts via atom trapping. Science 353, 150–154 (2016).

  9. 9.

    Lin, L. et al. Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts. Nature 544, 80–83 (2017).

  10. 10.

    Yang, M. et al. Catalytically active Au-O(OH) x -species stabilized by alkali ions on zeolites and mesoporous oxides. Science 346, 1498–1501 (2014).

  11. 11.

    Fei, H. et al. Atomic cobalt on nitrogen-doped graphene for hydrogen generation. Nat. Commun. 6, 8668 (2015).

  12. 12.

    Corma, A. et al. Exceptional oxidation activity with size-controlled supported gold clusters of low atomicity. Nat. Chem. 5, 775–781 (2013).

  13. 13.

    Li, Z. Y., Yuan, Z., Li, X. N., Zhao, Y. X. & He, S. G. CO oxidation catalyzed by single gold atoms supported on aluminum oxide clusters. J. Am. Chem. Soc. 136, 14307–14313 (2014).

  14. 14.

    Zhai, Y. et al. Alkali-stabilized Pt-OHx species catalyze low-temperature water-gas shift reactions. Science 329, 1633–1636 (2010).

  15. 15.

    Kyriakou, G. et al. Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations. Science 335, 1209–1212 (2012).

  16. 16.

    Malta, G. et al. Identification of single-site gold catalysis in acetylene hydrochlorination. Science 355, 1399–1403 (2017).

  17. 17.

    Guo, X. et al. Direct, nonoxidative conversion of methane to ethylene, aromatics, and hydrogen. Science 344, 616–619 (2014).

  18. 18.

    Wei, H. et al. FeOx-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes. Nat. Commun. 5, 5634 (2014).

  19. 19.

    Matsubu, J. C., Yang, V. N. & Christopher, P. Isolated metal active site concentration and stability control catalytic CO2 reduction selectivity. J. Am. Chem. Soc. 137, 3076–3084 (2015).

  20. 20.

    Peterson, E. J. et al. Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina. Nat. Commun. 5, 4885 (2014).

  21. 21.

    Liu, P. et al. Photochemical route for synthesizing atomically dispersed palladium catalysts. Science 352, 797–801 (2016).

  22. 22.

    Wang, L. et al. Incorporating nitrogen atoms into cobalt nanosheets as a strategy to boost catalytic activity toward CO2 hydrogenation. Nat. Energy 2, 869–876 (2017).

  23. 23.

    Studt, F. et al. Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol. Nat. Chem. 6, 320–324 (2014).

  24. 24.

    Matsubu, J. C. et al. Adsorbate-mediated strong metal-support interactions in oxide-supported Rh catalysts. Nat. Chem. 9, 120–127 (2017).

  25. 25.

    Katte, S., Ramírez, P. J., Chen, J. G., Rodriguez, J. A. & Liu, P. Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts. Science 355, 1296–1299 (2017).

  26. 26.

    Khan, M. U. et al. Pt3Co octapods as superior catalysts of CO2 hydrogenation. Angew. Chem. Int. Ed. 55, 9548–9552 (2016).

  27. 27.

    Ding, K. et al. Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts. Science 350, 189–192 (2015).

  28. 28.

    Bazin, P., Saur, O., Lavalley, J. C., Daturi, M. & Blanchard, G. FT-IR study of CO adsorption on Pt/CeO2: characterisation and structural rearrangement of small Pt particles. Phys. Chem. Chem. Phys. 7, 187–194 (2005).

  29. 29.

    Asokan, C., DeRita, L. & Christopher, P. Using probe molecule FTIR spectroscopy to identify and characterize Pt-group metal based single atom catalysts. Chin. J. Catal. 38, 1473–1480 (2017).

  30. 30.

    Qiao, B. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 3, 634–641 (2011).

  31. 31.

    DeRita, L. et al. Catalyst architecture for stable single atom dispersion enables site-specific spectroscopic and reactivity measurements of CO adsorbed to Pt atoms, oxidized Pt clusters, and metallic Pt clusters on TiO2. J. Am. Chem. Soc. 139, 14150–14165 (2017).

  32. 32.

    Pozdnyakova, O. et al. Preferential CO oxidation in hydrogen (PROX) on ceria-supported catalysts, part i: oxidation state and surface species on Pt/CeO2 under reaction conditions. J. Catal. 237, 1–16 (2006).

  33. 33.

    Mudiyanselage, K. et al. Importance of the metal-oxide interface in catalysis: in situ studies of the water-gas shift reaction by ambient-pressure X-ray photoelectron spectroscopy. Angew. Chem. Int. Ed. 52, 5101–5105 (2013).

  34. 34.

    Prosvirin, I. P., Bukhtiyarov, A. V., Bluhm, H. & Bukhtiyarov, V. I. Application of near ambient pressure gas-phase X-ray photoelectron spectroscopy to the investigation of catalytic properties of copper in methanol oxidation. Appl. Surf. Sci. 363, 303–309 (2016).

  35. 35.

    Deng, X. et al. Surface chemistry of Cu in the presence of CO2 and H2O. Langmuir 24, 9474–9478 (2008).

  36. 36.

    Delley, B. An all-electron numerical method for solving the local density functional for polyatomic molecules. J. Chem. Phys. 92, 508–517 (1990).

  37. 37.

    Delley, B. From molecules to solids with the DMol3 approach. J. Chem. Phys. 113, 7756–7763 (2000).

  38. 38.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

  39. 39.

    Govind, N., Petersen, M., Fitzgerald, G., King-Smith, D. & Andzelm, J. A generalized synchronous transit method for transition state location. Comput. Mater. Sci. 28, 250–258 (2003).

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This work was supported by Collaborative Innovation Center of Suzhou Nano Science and Technology, Ministry of Science and Technology of the People’s Republic of China (2014CB932700 and 2016YFA0200602), National Natural Science Foundation of China (21573206 and 21473167), Key Research Program of Frontier Sciences of the Chinese Academy of Sciences (QYZDB-SSW-SLH017), Anhui Provincial Key Scientific and Technological Project (1704a0902013), Anhui Provincial Natural Science Foundation (1608085QB29), Major Program of Development Foundation of Hefei Center for Physical Science and Technology (2017FXZY002), Fundamental Research Funds for the Central Universities, Shanghai Supercomputing Center and Supercomputing Center at the University of Science and Technology of China.

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  1. These authors contributed equally: Hongliang Li, Liangbing Wang.


  1. Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei, China

    • Hongliang Li
    • , Liangbing Wang
    • , Yizhou Dai
    • , Zhengtian Pu
    • , Zhuohan Lao
    • , Yawei Chen
    • , Menglin Wang
    • , Xusheng Zheng
    • , Junfa Zhu
    • , Wenhua Zhang
    • , Chao Ma
    •  & Jie Zeng
  2. Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, China

    • Rui Si


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H.L., L.W. and J.Zeng designed the studies and wrote the paper. H.L., L.W., Y.D. and Z.P. synthesized the catalysts. H.L., L.W., Y.C., Z.L. and M.W. performed catalytic tests. C.M. conducted HAADF-STEM analysis. H.L. and W.Z. performed DFT calculations. L.W., X.Z. and J.Zhu conducted XPS measurements. R.S. conducted XAFS measurements. All authors discussed the results and commented on the manuscript.

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The authors declare no competing interests.

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Correspondence to Wenhua Zhang or Jie Zeng.

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