Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation


The recent availability of shale gas has led to a renewed interest in C–H bond activation as the first step towards the synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu-based catalysts are not practical due to high C–H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Using Pt/Cu single-atom alloys (SAAs), we examine C–H activation in a number of systems including methyl groups, methane and butane using a combination of simulations, surface science and catalysis studies. We find that Pt/Cu SAAs activate C–H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke-resistant C–H activation chemistry, with the added economic benefit that the precious metal is diluted at the atomic limit.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Methane evolution as a reporter of C–H activation in methyl groups on various surface structures (experiment and simulation).
Figure 2: Comparison of the reaction pathways between pure and SAA surfaces.
Figure 3: STM imaging of reaction intermediates on Cu(111) and Pt/Cu SAA surfaces revealing lower-temperature C–H activation on Pt/Cu SAAs than Cu.
Figure 4: Reactor studies of B–D scrambling as a reporter of C–H activation and long-term catalyst stability of nanoparticle catalysts.
Figure 5: Oxidation tests reveal a lack of coking of Pt/Cu SAA catalysts.


  1. 1

    Sattler, J. J. H. B., Ruiz-Martinez, J., Santillan-Jimenez, E. & Weckhuysen, B. M. Catalytic dehydrogenation of light alkanes on metals and metal oxides. Chem. Rev. 114, 10613–10653 (2014).

    CAS  PubMed  Google Scholar 

  2. 2

    Alper, J. The Changing Landscape of Hydrocarbon Feedstocks for Chemical Production: Implications for Catalysis: Proceedings of a Workshop (The National Academies Press, 2016).

    Google Scholar 

  3. 3

    Shilov, A. E. & Shul'pin, G. B. Activation of C–H bonds by metal complexes. Chem. Rev. 97, 2879–2932 (1997).

    CAS  PubMed  Google Scholar 

  4. 4

    Labinger, J. A. & Bercaw, J. E. Understanding and exploiting C–H bond activation. Nature 417, 507–514 (2002).

    CAS  PubMed  Google Scholar 

  5. 5

    Wencel-Delord, J. & Glorius, F. C–H bond activation enables the rapid construction and late-stage diversification of functional molecules. Nat. Chem. 5, 369–375 (2013).

    CAS  PubMed  Google Scholar 

  6. 6

    Zhao, Z.-J., Chiu, C. & Gong, J. Molecular understandings on the activation of light hydrocarbons over heterogeneous catalysts. Chem. Sci. 6, 4403–4425 (2015).

    CAS  PubMed  PubMed Central  Google Scholar 

  7. 7

    Lin, R., Amrute, A. P. & Pérez-Ramírez, J. Halogen-mediated conversion of hydrocarbons to commodities. Chem. Rev. 117, 4182–4247 (2017).

    CAS  PubMed  Google Scholar 

  8. 8

    McFarland, E. Unconventional chemistry for unconventional natural gas. Science 338, 340–342 (2012).

    CAS  PubMed  Google Scholar 

  9. 9

    Gärtner, C. A., van Veen, A. C. & Lercher, J. A. Oxidative dehydrogenation of ethane: common principles and mechanistic aspects. ChemCatChem 5, 3196–3217 (2013).

    Google Scholar 

  10. 10

    Schwarz, H. Chemistry with methane: concepts rather than recipes. Angew. Chem. Int. Ed. 50, 10096–10115 (2011).

    CAS  Google Scholar 

  11. 11

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

    CAS  PubMed  Google Scholar 

  12. 12

    Schweitzer, N. M. et al. Propylene hydrogenation and propane dehydrogenation by a single-site Zn2+ on silica catalyst. ACS Catal. 4, 1091–1098 (2014).

    CAS  Google Scholar 

  13. 13

    Swaan, H. M., Kroll, V. C. H., Martin, G. A. & Mirodatos, C. Deactivation of supported nickel catalysts during the reforming of methane by carbon dioxide. Catal. Today 21, 571–578 (1994).

    CAS  Google Scholar 

  14. 14

    Ruckenstein, E. & Hu, Y. H. Carbon dioxide reforming of methane over nickel/alkaline earth metal oxide catalysts. Appl. Catal. A 133, 149–161 (1995).

    CAS  Google Scholar 

  15. 15

    Taccardi, N. et al. Gallium-rich Pd–Ga phases as supported liquid metal catalysts. Nat. Chem. 9, 862–867 (2017).

    CAS  PubMed  Google Scholar 

  16. 16

    Jiang, F. et al. Propane dehydrogenation over Pt/TiO2–Al2O3 catalyst. ACS Catal. 5, 438–447 (2015).

    CAS  Google Scholar 

  17. 17

    Iglesias-Juez, A. et al. A combined in situ time-resolved UV-vis, Raman and high-energy resolution X-ray absorption spectroscopy study on the deactivation behavior of Pt and PtSn propane dehydrogenation catalysts under industrial reaction conditions. J. Catal. 276, 268–279 (2010).

    CAS  Google Scholar 

  18. 18

    Henderson, M. A., Mitchell, G. E. & White, J. M. The chemisorption of methyl halides (Cl, Br, and I) on Pt(111). Surf. Sci. 184, L325–L331 (1987).

    Google Scholar 

  19. 19

    Yang, F., Koeller, J. & Ackermann, L. Photoinduced copper-catalyzed C–H arylation at room temperature. Angew. Chem. Int. Ed. 55, 4759–4762 (2016).

    Google Scholar 

  20. 20

    Besenbacher, F. et al. Design of a surface alloy catalyst for steam reforming. Science 279, 1913–1915 (1998).

    CAS  PubMed  Google Scholar 

  21. 21

    Rodriguez, J. A. Physical and chemical properties of bimetallic surfaces. Surf. Sci. Rep. 24, 223–287 (1996).

    CAS  Google Scholar 

  22. 22

    Lucci, F. R., Marcinkowski, M. D., Lawton, T. J. & Sykes, E. C. H. H2 activation and spillover on catalytically relevant Pt–Cu single atom alloys. J. Phys. Chem. C 119, 24351–24357 (2015).

    CAS  Google Scholar 

  23. 23

    Lucci, F. R. et al. Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit. Nat. Commun. 6, 8550 (2015).

    PubMed  PubMed Central  Google Scholar 

  24. 24

    Lucci, F. R., Lawton, T. J., Pronschinske, A. & Sykes, E. C. H. Atomic scale surface structure of Pt/Cu(111) surface alloys. J. Phys. Chem C. 118, 3015–3022 (2014).

    CAS  Google Scholar 

  25. 25

    Yang, X. F. et al. Single-atom catalysts: a new frontier in heterogeneous catalysis. Acc. Chem. Res. 46, 1740–1748 (2013).

    CAS  PubMed  Google Scholar 

  26. 26

    Thomas, J. M., Saghi, Z. & Gai, P. L. Can a single atom serve as the active site in some heterogeneous catalysts? Top. Catal. 54, 588–594 (2011).

    CAS  Google Scholar 

  27. 27

    Azizian, S. & Gobal, F. Mechanism of catalytic decomposition of CH3I on the Cu(111) surface: a UBI-QEP approach. Langmuir 16, 8095–8099 (2000).

    CAS  Google Scholar 

  28. 28

    Chiang, C. -M., Wentzlaff, T. H. & Bent, B. E. Iodomethane decomposition on copper(110): surface reactions of C1 fragments. J. Phys. Chem. 96, 1836–1848 (1992).

    CAS  Google Scholar 

  29. 29

    French, C. & Harrison, I. Orientation and decomposition kinetics of methyl iodide on Pt(111). Surf. Sci. 342, 85–100 (1995).

    CAS  Google Scholar 

  30. 30

    Lin, J.-L. & Bent, B. E. Iodomethane dissociation on Cu(111): bonding and chemistry of adsorbed methyl groups. J. Vac. Sci. Technol. A 10, 2202–2209 (1992).

    CAS  Google Scholar 

  31. 31

    Lin, J.-L. & Bent, B. E. Two mechanisms for formation of methyl radicals during the thermal decomposition of CH3I on a Cu(111) surface. J. Phys. Chem. 97, 9713–9718 (1993).

    CAS  Google Scholar 

  32. 32

    Zaera, F. Study of the surface chemistry of methyl iodide coadsorbed with hydrogen on Pt(111). Surf. Sci. 262, 335–350 (1992).

    CAS  Google Scholar 

  33. 33

    Pascal, M. et al. Methyl on Cu(111)–structural determination including influence of co-adsorbed iodine. Surf. Sci. 512, 173–184 (2002).

    CAS  Google Scholar 

  34. 34

    Chao-Ming, C. & Bent, B. E. Methyl radical adsorption on Cu(111): bonding, reactivity, and the effect of coadsorbed iodine. Surf. Sci. 279, 79–88 (1992).

    Google Scholar 

  35. 35

    Canning, N. D. S., Baker, M. D. & Chesters, M. A. Ethylene and acetylene adsorption on Cu(111) and Pt(111) studied by Auger spectroscopy. Surf. Sci. 111, 441–451 (1981).

    CAS  Google Scholar 

  36. 36

    Meyers, J. M. & Gellman, A. J. The investigation of fluorinated propenes on the Cu(111) surface. Surf. Sci. 339, 57–67 (1995).

    CAS  Google Scholar 

  37. 37

    Liu, J. et al. Tackling CO poisoning with single atom alloy catalysts. J. Am. Chem. Soc. 138, 6396–6399 (2016).

    CAS  PubMed  Google Scholar 

  38. 38

    Henkelman, G. & Jónsson, H. A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives. J. Chem. Phys. 111, 7010–7022 (1999).

    CAS  Google Scholar 

  39. 39

    Henkelman, G. & Jónsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978–9985 (2000).

    CAS  Google Scholar 

  40. 40

    Psofogiannakis, G., St-Amant, A. & Ternan, M. Methane oxidation mechanism on Pt(111): a cluster model DFT study. J. Phys. Chem. B 110, 24593–24605 (2006).

    CAS  PubMed  Google Scholar 

  41. 41

    Chan, Y. L., Pai, W. W. & Chuang, T. J. Direct observation of methyl radicals islanding on copper surfaces and its effects on the kinetics of catalytic reactions. J. Phys. Chem. B 108, 815–818 (2004).

    CAS  Google Scholar 

  42. 42

    Michaelides, A. & Hu, P. Softened C–H modes of adsorbed methyl and their implications for dehydrogenation: an ab initio study. J. Chem. Phys. 114, 2523–2526 (2001).

    CAS  Google Scholar 

  43. 43

    Andryushechkin, B. V., Eltsov, K. N. & Shevlyuga, V. M. Atomic scale observation of iodine layer compression on Cu(111). Surf. Sci. 472, 80–88 (2001).

    CAS  Google Scholar 

  44. 44

    Deng, W. & Flytzani-Stephanopoulos, M. On the issue of the deactivation of Au–ceria and Pt–ceria water–gas shift catalysts in practical fuel-cell applications. Angew. Chem. 118, 2343–2347 (2006).

    Google Scholar 

  45. 45

    Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    CAS  Google Scholar 

  46. 46

    Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    CAS  Google Scholar 

  47. 47

    Klimeš, J., Bowler, D. R. & Michaelides, A. Van der Waals density functionals applied to solids. Phys. Rev. B 83, 195131 (2011).

    Google Scholar 

  48. 48

    Dion, M., Rydberg, H., Schröder, E., Langreth, D. C. & Lundqvist, B. I. Van der Waals density functional for general geometries. Phys. Rev. Lett. 92, 246401 (2004).

    CAS  PubMed  Google Scholar 

  49. 49

    Stamatakis, M. & Vlachos, D. G. A graph-theoretical kinetic Monte Carlo framework for on-lattice chemical kinetics. J. Chem. Phys. 134, 214115 (2011).

    PubMed  Google Scholar 

  50. 50

    Nielsen, J., D'Avezac, M., Hetherington, J. & Stamatakis, M. Parallel kinetic Monte Carlo simulation framework incorporating accurate models of adsorbate lateral interactions. J. Chem. Phys. 139, 224706 (2013).

    PubMed  Google Scholar 

  51. 51

    Marcinkowski, M. D. et al. Selective formic acid dehydrogenation on Pt-Cu single-atom alloys. ACS Catal. 7, 413–420 (2017).

    CAS  Google Scholar 

  52. 52

    Boucher, M. B. et al. Single atom alloy surface analogs in Pd0.18Cu15 nanoparticles for selective hydrogenation reactions. Phys. Chem. Chem. Phys. 15, 12187–12196 (2013).

    CAS  PubMed  Google Scholar 

Download references


All surface science studies (M.D.M., F.R.L. and E.C.H.S.) were performed with support from the Division of Chemical Sciences, Office of Basic Energy Sciences, CPIMS Program, US Department of Energy, under grant no. FG02-10ER16170. J.L. and M.F-S. acknowledge the US Department of Energy (DE-FG02-05ER15730) for financial support of the catalysis work. The X-ray absorption spectroscopy research used resources of the Advanced Photon Source, a US Department of Energy Office of Science, User Facility operated for the Department of Energy Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. M.T.D is funded by the Engineering and Physical Sciences Research Council UK as part of a Doctoral Training Grant (Award Ref. 1352369). The authors acknowledge the use of the UCL High Performance Computing Facilities (Legion@UCL and Grace@UCL) and associated support services, in the completion of the computational part of this work. The theoretical portion of the research also used resources of the Oak Ridge Leadership Computing Facility, which is a DOE Office of Science User Facility supported under contract no. DE-AC05-00OR22725. Access to the Oak Ridge facility was provided via the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences under award #DE-SC0012573. The development of software Zacros has been funded under the embedded Computer Science and Engineering (eCSE) programme of the ARCHER UK National Supercomputing Service (eCSE01-001, eCSE10-8). A.M. is supported by the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013)–European Research Council grant agreement no. 616121 (HeteroIce project). A.M. is also supported by the Royal Society through a Royal Society Wolfson Research Merit Award.

Author information




M.D.M. performed the TPR experiments. M.T.D. performed the DFT and KMC calculations. M.D.M. and F.R.L. performed the STM experiments. J.L. and J.M.W. performed the nanoparticle experiments. S.L. performed the EXAFS measurements. M.D.M., M.T.D. and J.L. analysed the data from their relevant experimental/theoretical contributions. M.D.M., M.T.D., J.L., A.M., M.F.-S., M.S. and E.C.H.S. wrote the manuscript. All authors read and commented on the manuscript.

Corresponding authors

Correspondence to Maria Flytzani-Stephanopoulos or Michail Stamatakis or E. Charles H. Sykes.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 3207 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Marcinkowski, M., Darby, M., Liu, J. et al. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation. Nature Chem 10, 325–332 (2018).

Download citation

Further reading


Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing