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Direct methane activation by atomically thin platinum nanolayers on two-dimensional metal carbides

Nature Catalysis volume 4, pages 882–891 (2021)Cite this article

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Abstract

Efficient and direct conversion of methane to value-added products has been a long-term challenge in shale gas applications. Here, we show that atomically thin nanolayers of Pt with a single or double atomic layer thickness, supported on a two-dimensional molybdenum titanium carbide (MXene), catalyse non-oxidative coupling of methane to ethane/ethylene (C2). Kinetic and theoretical studies, combined with in-situ spectroscopic and microscopic characterizations, demonstrate that Pt nanolayers anchored at the hexagonal close-packed sites of the MXene support can activate the first C–H bond of methane to form methyl radicals that favour desorption over further dehydrogenation and thus suppress coke deposition. At 750 °C and 7% methane conversion, the catalyst runs for 72 hours of continuous operation without deactivation and exhibits >98% selectivity towards C2 products, with a turnover frequency of 0.2–0.6 s−1. Our findings provide insights into the design of highly active and stable catalysts for methane activation and create a platform for developing atomically thin supported metal catalysts.

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Fig. 1: Atomic structure and DFT calculations of Pt supported by Mo2TiC2Tx MXene.
Fig. 2: Catalytic performance of Pt/Mo2TiC2Tx for non-oxidative coupling of methane.
Fig. 3: Structural characterization of 0.5% Pt/Mo2TiC2Tx catalysts reduced at 750 °C.
Fig. 4: Oxidation tests and DFT calculations.

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Data availability

The data that support the findings of this study are deposited at https://iastate.box.com/s/sf9go743qngg8ta0ufni0q102nu7hvjv. All the data and access are available from the corresponding authors on reasonable request.

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Acknowledgements

Y.W. appreciates the support from the Herbert L. Stiles Professorship and Iowa State University College of Engineering exploratory research projects. J.C.Z., Z.W. and J.T.M. were supported in part by the National Science Foundation under Cooperative Agreement no. EEC-1647722. Y.X. and A.V. thank the R. Games Slayter Fund and the Varma Reaction Engineering Research Fund of Purdue University. Z.Z. and J.P.G. acknowledge financial support from NSF-CBET Award 1804712. T.M. acknowledges the financial support of the University of Michigan College of Engineering and technical support from the Michigan Center for Materials Characterization. Use of the Advanced Photon Source was supported by the US Department of Energy, Office of Basic Energy Sciences under contract no. DE-AC02-06CH11357. MRCAT operations, beamline 10-BM, are supported by the Department of Energy and the MRCAT member institutions. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. All TEM-related work was performed using instruments in the Sensitive Instrument Facility in Ames Laboratory. Ames Laboratory is operated for the US Department of Energy by Iowa State University under contract no. DE-AC02-07CH11358.

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Author notes

  1. Tae-Hoon Kim

    Present address: Department of Materials Science and Engineering, Chonnam National University, Gwangju, South Korea

  2. These authors contributed equally Zhe Li, Yang Xiao.

  3. Deceased: Arvind Varma.

Authors and Affiliations

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

    Zhe Li, Peilei He & Yue Wu

  2. Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN, USA

    Yang Xiao, Zhenwei Wu, Johnny Zhu Chen, Pratik J. Potdar, Zhenhua Zeng, Jeffrey T. Miller, Jeffrey P. Greeley & Arvind Varma

  3. School of Mechanical Engineering and the Birck Nanotechnology Center, Purdue University, West Lafayette, IN, USA

    Prabudhya Roy Chowdhury & Xiulin Ruan

  4. Department of Energy Ames Laboratory, Ames, IA, USA

    Tao Ma, Tae-Hoon Kim, Dapeng Jing & Lin Zhou

  5. SLAC National Accelerator Laboratory, Stanford University, Menlo Park, CA, USA

    Gang Wan

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Contributions

Z.L. and Y.X. conceived the idea and designed the present work. Y.X., P.R.C. and Z.Z. conducted DFT calculations. Z.L., Y.X., P.J.P. and P.H. synthesized the catalysts and performed the catalytic evaluation. J.Z.C., Z.W., G.W., D.J. and J.T.M. carried out the spectroscopic characterizations. L.Z., T.M., T.-H.K. and Z.L. performed the detailed microscopic experiments. Y.W., J.T.M., X.R., J.P.G. and A.V. supervised the research.

Corresponding authors

Correspondence to Yang Xiao or Yue Wu.

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Competing interests

Z.L., Y.W. and X.Y. are inventors on US. Provisional Patent Application 62/937,055, submitted by Iowa State University. The remaining authors declare no competing interests.

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Peer review information Nature Catalysis thanks Chen Chen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Notes 1–3, Figs. 1–36, Tables 1–8,and refs. 1–5,

Supplementary Data 1

Atomic coordinates of optimized structures for DFT calculations conducted in this study

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Li, Z., Xiao, Y., Chowdhury, P.R. et al. Direct methane activation by atomically thin platinum nanolayers on two-dimensional metal carbides. Nat Catal 4, 882–891 (2021). https://doi.org/10.1038/s41929-021-00686-y

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