Article | Published:

Reactive metal–support interactions at moderate temperature in two-dimensional niobium-carbide-supported platinum catalysts

Nature Catalysisvolume 1pages349355 (2018) | Download Citation


The reactive metal–support interaction (RMSI) offers electronic, geometric and compositional effects that can be used to tune catalytic active sites. Generally, supports other than oxides are disregarded as candidates for RMSI. Here, we report an example of non-oxide-based RMSI between platinum and Nb2CT x MXene—a recently developed, two-dimensional metal carbide. The surface functional groups of the two-dimensional carbide can be reduced, and a Pt–Nb surface alloy is formed at a moderate temperature (350 °C). Such an alloy exhibits weaker CO adsorption than monometallic platinum. Water-gas shift reaction kinetics reveals that the RMSI stabilizes the nanoparticles and creates alloy–MXene interfaces with higher H2O activation ability compared with a non-reducible support or a bulk niobium carbide. This RMSI between platinum and the niobium MXene support can be extended to other members of the MXene family and opens new avenues for the facile design and manipulation of functional bimetallic catalysts.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Additional information

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


  1. 1.

    Yu, W., Porosoff, M. D. & Chen, J. G. Review of Pt-based bimetallic catalysis: from model surfaces to supported catalysts. Chem. Rev. 112, 5780–5817 (2012).

  2. 2.

    Sankar, M. et al. Designing bimetallic catalysts for a green and sustainable future. Chem. Soc. Rev. 41, 8099–8139 (2012).

  3. 3.

    Wang, H., Wang, C., Yan, H., Yi, H. & Lu, J. Precisely-controlled synthesis of Au@Pd core–shell bimetallic catalyst via atomic layer deposition for selective oxidation of benzyl alcohol. J. Catal. 324, 59–68 (2015).

  4. 4.

    Armbrüster, M. Intermetallic Compounds in Catalysis, Encyclopedia of Catalysis (Wiley, Weinheim, 2011).

  5. 5.

    Penner, S. & Armbrüster, M. Formation of intermetallic compounds by reactive metal–support interaction: a frequently encountered phenomenon in catalysis. ChemCatChem 7, 374–392 (2015).

  6. 6.

    Wang, D. et al. Silicide formation on a Pt/SiO2 model catalyst studied by TEM, EELS, and EDXS. J. Catal. 219, 434–441 (2003).

  7. 7.

    Penner, S. et al. Platinum nanocrystals supported by silica, alumina and ceria: metal–support interaction due to high-temperature reduction in hydrogen. Surf. Sci. 532, 276–280 (2003).

  8. 8.

    Lukatskaya, M. R. et al. Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide. Science 341, 1502–1505 (2013).

  9. 9.

    Naguib, M., Mochalin, V. N., Barsoum, M. W. & Gogotsi, Y. 25th anniversary article: MXenes: a new family of two-dimensional materials. Adv. Mater. 26, 992–1005 (2014).

  10. 10.

    Anasori, B., Lukatskaya, M. R. & Gogotsi, Y. 2D metal carbides and nitrides (MXenes) for energy storage. Nat. Rev. Mater. 2, 16098 (2017).

  11. 11.

    Ma, T. Y., Cao, J. L., Jaroniec, M. & Qiao, S. Z. Interacting carbon nitride and titanium carbide nanosheets for high-performance oxygen evolution. Angew. Chem. Int. Ed. 55, 1138–1142 (2016).

  12. 12.

    Ran, J. et al. Ti3C2 MXene co-catalyst on metal sulfide photo-absorbers for enhanced visible-light photocatalytic hydrogen production. Nat. Commun. 8, 13907 (2017).

  13. 13.

    Schreier, M. & Regalbuto, J. R. A fundamental study of Pt tetraammine impregnation of silica: 1. The electrostatic nature of platinum adsorption. J. Catal. 225, 190–202 (2004).

  14. 14.

    Lambert, S. et al. Synthesis of very highly dispersed platinum catalysts supported on carbon xerogels by the strong electrostatic adsorption method. J. Catal. 261, 23–33 (2009).

  15. 15.

    Lu, J., Zhang, X., Bravo-Suarez, J. J., Fujitani, T. & Oyama, S. T. Effect of composition and promoters in Au/TS-1 catalysts for direct propylene epoxidation using H2 and O2. Catal. Today 147, 186–195 (2009).

  16. 16.

    Rakhi, R., Ahmed, B., Hedhili, M. N., Anjum, D. H. & Alshareef, H. N. Effect of postetch annealing gas composition on the structural and electrochemical properties of Ti2CT x MXene electrodes for supercapacitor applications. Chem. Mater. 27, 5314–5323 (2015).

  17. 17.

    Naguib, M. et al. New two-dimensional niobium and vanadium carbides as promising materials for Li-ion batteries. J. Am. Chem. Soc. 135, 15966–15969 (2013).

  18. 18.

    Sabnis, K. D. et al. Water-gas shift catalysis over transition metals supported on molybdenum carbide. J. Catal. 331, 162–171 (2015).

  19. 19.

    Shekhar, M. Water-Gas Shift Catalysis Over Supported Gold and Platinum Nanoparticles PhD thesis, Purdue Univ. (2012).

  20. 20.

    Sabnis, K. D. et al. Probing the active sites for water-gas shift over Pt/molybdenum carbide using multi-walled carbon nanotubes. J. Catal. 330, 442–451 (2015).

  21. 21.

    Balakrishnan, K. & Schwank, J. A chemisorption and XPS study of bimetallic Pt–Sn/Al2O3 catalysts. J. Catal. 127, 287–306 (1991).

  22. 22.

    Wakisaka, M. et al. Electronic structures of Pt–Co and Pt–Ru alloys for CO-tolerant anode catalysts in polymer electrolyte fuel cells studied by EC-XPS. J. Phys. Chem. B 110, 23489–23496 (2006).

  23. 23.

    Beard, B. C. & Ross, P. N. Platinum–titanium alloy formation from high-temperature reduction of a titania-impregnated platinum catalyst: implications for strong metal–support interaction. J. Phys. Chem. 90, 6811–6817 (1986).

  24. 24.

    Hammer, B., Morikawa, Y. & Nørskov, J. K. CO chemisorption at metal surfaces and overlayers. Phys. Rev. Lett. 76, 2141–2144 (1996).

  25. 25.

    Gauthier, Y. et al. Adsorption sites and ligand effect for CO on an alloy surface: a direct view. Phys. Rev. Lett. 87, 036103 (2001).

  26. 26.

    Schaidle, J. A., Schweitzer, N. M., Ajenifujah, O. T. & Thompson, L. T. On the preparation of molybdenum carbide-supported metal catalysts. J. Catal. 289, 210–217 (2012).

  27. 27.

    Cui, Y. et al. Participation of interfacial hydroxyl groups in the water-gas shift reaction over Au/MgO catalysts. Catal. Sci. Technol. 7, 5257–5266 (2017).

  28. 28.

    Hu, C. et al. In situ reaction synthesis, electrical and thermal, and mechanical properties of Nb4AlC3. J. Am. Ceram. Soc. 91, 2258–2263 (2008).

  29. 29.

    Wang, X. & Zhou, Y. Microstructure and properties of Ti3AlC2 prepared by the solid–liquid reaction synthesis and simultaneous in-situ hot pressing process. Acta Mater. 50, 3143–3151 (2002).

  30. 30.

    Bollmann, L. et al. Effect of Zn addition on the water-gas shift reaction over supported palladium catalysts. J. Catal. 257, 43–54 (2008).

Download references


Y.W. appreciates support from the Herbert L. Stiles Professorship and the ACRI Center Initiative at Iowa State University. F.H.R. acknowledges the partial support provided by the National Science Foundation. This paper is based on work supported in part by the National Science Foundation under cooperative agreement EEC-1647722. Any opinions, findings and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation.

Author information

Author notes

  1. These authors contributed equally: Zhe Li, Yanran Cui, Zhenwei Wu.


  1. Department of Chemical and Biological Engineering, Iowa State University, Ames, IA, USA

    • Zhe Li
    • , Biao Xu
    • , Enzheng Shi
    •  & Yue Wu
  2. Charles D. Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN, USA

    • Yanran Cui
    • , Zhenwei Wu
    • , Cory Milligan
    • , Garrett Mitchell
    • , Jeffrey T. Miller
    •  & Fabio H. Ribeiro
  3. Department of Energy, Ames Laboratory, Ames, IA, USA

    • Lin Zhou


  1. Search for Zhe Li in:

  2. Search for Yanran Cui in:

  3. Search for Zhenwei Wu in:

  4. Search for Cory Milligan in:

  5. Search for Lin Zhou in:

  6. Search for Garrett Mitchell in:

  7. Search for Biao Xu in:

  8. Search for Enzheng Shi in:

  9. Search for Jeffrey T. Miller in:

  10. Search for Fabio H. Ribeiro in:

  11. Search for Yue Wu in:


Z.L. conceived the research and performed the synthesis and material characterizations. Y.C. and F.H.R. carried out the CO chemisorption and WGS kinetics measurements. Z.W. and J.T.M. carried out the XAS measurements. L.Z., G.M., B.X. and E.S. conducted microscopy analyses. C.M. performed the XPS experiments. Y.W. supervised and led the project.

Competing interests

The authors have filed a patent application (US Patent application no. 62/579,364).

Corresponding author

Correspondence to Yue Wu.

Supplementary information

  1. Supplementary Information

    Supplementary Methods; Supplementary Figures 1–13; Supplementary Table 1; Supplementary References

About this article

Publication history




Issue Date


Further reading