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Interface-mediated noble metal deposition on transition metal dichalcogenide nanostructures

Nature Chemistry volume 12, pages 284–293 (2020)Cite this article

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Abstract

Functionalizing the surfaces of transition metal dichalcogenide (TMD) nanosheets with noble metals is important for electrically contacting them to devices, as well as improving their catalytic and sensing capabilities. Solution-phase deposition provides a scalable approach to the creation of metal–TMD hybrid systems, but controlling such processes remains challenging. Here we elucidate the different pathways by which gold and silver deposit at room temperature onto colloidal 1T-WS2, 2H-WS2, 2H-MoSe2, 2H-WSe2, 1T′-MoTe2 and Td-WTe2 few-layer nanostructures to produce several distinct classes of 0D–2D and 2D–2D metal–TMD hybrids. Uniform gold nanoparticles form on all of the TMDs. By contrast, silver deposits as nanoparticles with a bimodal size distribution on the disulfides and diselenides, and as atomically thin layers on the ditellurides. The various sizes and morphologies of these surface-bound metal species arise from the relative strengths of the interfacial metal–chalcogen bonds during the reduction of Au3+ or Ag+ by the TMDs.

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Fig. 1: Reduction of Au3+ on TMD nanostructures.
Fig. 2: The influence of electronic structure and structural defects on the reduction of Au3+ on TMD nanostructures.
Fig. 3: Reduction of Ag+ on TMD nanostructures.
Fig. 4: Microscopic evidence of atomic Ag layers deposited on the 1T′-MoTe2 nanostructures.
Fig. 5: Spectroscopic investigation of Ag/1 T′-MoTe2 and Ag/WTe2.
Fig. 6: DFT calculations for noble metal–TMD systems.

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All of the data that support the findings of this study are available within the Article and its Supplementary Information, and/or from the corresponding author on reasonable request.

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Acknowledgements

Y.S. and R.E.S. were supported by the US National Science Foundation grant DMR-1607135 for the initial synthesis of the TMD nanostructures and grant CHE-1707830 for the studies involving deposition of Au and Ag. Y.W. and V.H.C. acknowledge the National Science Foundation Materials Innovation Platform Two-Dimensional Crystal Consortium under grant no. DMR-1539916. J.Y.C.C. and C.F.H. were supported by funds from Penn State University. Y.S., K.F. and M.T. acknowledge support from the Air Force Office of Scientific Research (AFOSR) grant FA9550-18-1-0072. J.T.M. was supported by the National Science Foundation under Cooperative Agreement no. EEC‐1647722. V.H.C. and M.T. also acknowledge the Center for 2-Dimensional and Layered Materials at the Pennsylvania State University. Electron microscopy and XPS were performed at the Electron Microscopy Facility at the Materials Characterization Lab of the Penn State Materials Research Institute. Use of APS is supported by the US Department of Energy, Office of Science, and 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. We thank J. Katsoudas and J. Wright for the assistance during XAS experiments at the 10-BM beamline at the APS at Argonne National Laboratory. We also thank J. Grey and K. Wang for assistance with TEM characterization and J. Shallenberger for XPS acquisition and analysis.

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Authors and Affiliations

  1. Department of Chemistry, The Pennsylvania State University, University Park, PA, USA

    Yifan Sun, Jamie Y. C. Chen, Cameron F. Holder, Vincent H. Crespi, Mauricio Terrones & Raymond E. Schaak

  2. Materials Research Institute, The Pennsylvania State University, University Park, PA, USA

    Yifan Sun, Yuanxi Wang, Kazunori Fujisawa, Vincent H. Crespi, Mauricio Terrones & Raymond E. Schaak

  3. Center for 2-Dimensional and Layered Materials, The Pennsylvania State University, University Park, PA, USA

    Yifan Sun, Yuanxi Wang, Kazunori Fujisawa, Vincent H. Crespi & Mauricio Terrones

  4. Department of Physics, The Pennsylvania State University, University Park, PA, USA

    Yuanxi Wang, Kazunori Fujisawa, Vincent H. Crespi & Mauricio Terrones

  5. 2-Dimensional Crystal Consortium, The Pennsylvania State University, University Park, PA, USA

    Yuanxi Wang & Vincent H. Crespi

  6. Charles D. Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN, USA

    Jeffery T. Miller

  7. Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA, USA

    Vincent H. Crespi & Mauricio Terrones

  8. Department of Chemical Engineering, The Pennsylvania State University, University Park, PA, USA

    Raymond E. Schaak

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Contributions

Y.S. carried out all the synthetic work and characterization by XRD, TEM, HAADF-STEM, STEM-EDS and Raman. Y.W. and V.H.C. performed the DFT calculations. J.Y.C.C., C.F.H. and Y.S. conducted the XAS measurements. J.Y.C.C. and J.T.M. analysed EXAFS and XANES data. C.F.H. also carried out XPS acquisition and analysis for part of the samples. K.F. carried out the high-resolution ADF-STEM imaging and simulation. M.T. and R.E.S. conceived and directed the project. Y.S., Y.W., J.Y.C.C., V.H.C., M.T. and R.E.S. prepared the manuscript.

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Correspondence to Vincent H. Crespi, Mauricio Terrones or Raymond E. Schaak.

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Supplementary Information

Additional experimental and calculation details, Supplementary Tables 1–5, Figs. 1–34 and refs. 1–25.

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Sun, Y., Wang, Y., Chen, J.Y.C. et al. Interface-mediated noble metal deposition on transition metal dichalcogenide nanostructures. Nat. Chem. 12, 284–293 (2020). https://doi.org/10.1038/s41557-020-0418-3

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