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

Abstract

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.

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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.

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Acknowledgements

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.

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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.

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

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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). https://doi.org/10.1038/nchem.2915

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