Abstract
Crystal phase is a key factor determining the properties, and hence functions, of two-dimensional transition-metal dichalcogenides (TMDs)1,2. The TMD materials, explored for diverse applications3,4,5,6,7,8, commonly serve as templates for constructing nanomaterials3,9 and supported metal catalysts4,6,7,8. However, how the TMD crystal phase affects the growth of the secondary material is poorly understood, although relevant, particularly for catalyst development. In the case of Pt nanoparticles on two-dimensional MoS2 nanosheets used as electrocatalysts for the hydrogen evolution reaction7, only about two thirds of Pt nanoparticles were epitaxially grown on the MoS2 template composed of the metallic/semimetallic 1T/1T′ phase but with thermodynamically stable and poorly conducting 2H phase mixed in. Here we report the production of MoS2 nanosheets with high phase purity and show that the 2H-phase templates facilitate the epitaxial growth of Pt nanoparticles, whereas the 1T′ phase supports single-atomically dispersed Pt (s-Pt) atoms with Pt loading up to 10 wt%. We find that the Pt atoms in this s-Pt/1T′-MoS2 system occupy three distinct sites, with density functional theory calculations indicating for Pt atoms located atop of Mo atoms a hydrogen adsorption free energy of close to zero. This probably contributes to efficient electrocatalytic H2 evolution in acidic media, where we measure for s-Pt/1T′-MoS2 a mass activity of 85 ± 23 A \({\text{mg}}_{\text{Pt}}^{-1}\) at the overpotential of −50 mV and a mass-normalized exchange current density of 127 A \({\text{mg}}_{\text{Pt}}^{-1}\) and we see stable performance in an H-type cell and prototype proton exchange membrane electrolyser operated at room temperature. Although phase stability limitations prevent operation at high temperatures, we anticipate that 1T′-TMDs will also be effective supports for other catalysts targeting other important reactions.
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Data availability
All data that support the findings of this study are available from the corresponding author upon reasonable request. Source data are provided with this paper.
References
Chhowalla, M. et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 5, 263–275 (2013).
Chen, Y. et al. Phase engineering of nanomaterials. Nat. Rev. Chem. 4, 243–256 (2020).
Novoselov, K. S., Mishchenko, A., Carvalho, A. & Castro Neto, A. H. 2D materials and van der Waals heterostructures. Science 353, aac9439 (2016).
Liu, G. et al. MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction. Nat. Chem. 9, 810–816 (2017).
Geim, A. K. & Grigorieva, I. V. Van der Waals heterostructures. Nature 499, 419–425 (2013).
Li, H. et al. Synergetic interaction between neighbouring platinum monomers in CO2 hydrogenation. Nat. Nanotechnol. 13, 411–417 (2018).
Huang, X. et al. Solution-phase epitaxial growth of noble metal nanostructures on dispersible single-layer molybdenum disulfide nanosheets. Nat. Commun. 4, 1444 (2013).
Shi, Y. et al. Site-specific electrodeposition enables self-terminating growth of atomically dispersed metal catalysts. Nat. Commun. 11, 4558 (2020).
Sun, Y. et al. Interface-mediated noble metal deposition on transition metal dichalcogenide nanostructures. Nat. Chem. 12, 284–293 (2020).
Yu, Y. et al. High phase-purity 1T′-MoS2- and 1T′-MoSe2-layered crystals. Nat. Chem. 10, 638–643 (2018).
Liu, L. et al. Phase-selective synthesis of 1T′ MoS2 monolayers and heterophase bilayers. Nat. Mater. 17, 1108–1114 (2018).
Lin, Z. et al. Solution-processable 2D semiconductors for high performance large-area electronics. Nature 562, 254–258 (2018).
Coleman, J. N. et al. Two-dimensional nanosheets produced by liquid exfoliation of layered materials. Science 331, 568–571 (2011).
Peng, J. et al. High phase purity of large-sized 1T′-MoS2 monolayers with 2D superconductivity. Adv. Mater. 31, 1900568 (2019).
Shen, R. et al. High-concentration single atomic Pt sites on hollow CuSx for selective O2 reduction to H2O2 in acid solution. Chem 5, 2099–2110 (2019).
Qiao, B. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 3, 634–641 (2011).
Ren, Y. et al. Unraveling the coordination structure-performance relationship in Pt1/Fe2O3 single-atom catalyst. Nat. Commun. 10, 4500 (2019).
Borodko, Y., Ercius, P., Pushkarev, V., Thompson, C. & Somorjai, G. From single Pt atoms to Pt nanocrystals: photoreduction of Pt2+ inside of a PAMAM dendrimer. J. Phys. Chem. Lett. 3, 236–241 (2012).
Hansen, J. N. et al. Is there anything better than Pt for HER? ACS Energy Lett. 6, 1175–1180 (2021).
Zheng, J., Yan, Y. & Xu, B. Correcting the hydrogen diffusion limitation in rotating disk electrode measurements of hydrogen evolution reaction kinetics. J. Electrochem. Soc. 162, F1470–F1481 (2015).
Zalitis, C. M., Sharman, J., Wright, E. & Kucernak, A. R. Properties of the hydrogen oxidation reaction on Pt/C catalysts at optimised high mass transport conditions and its relevance to the anode reaction in PEFCs and cathode reactions in electrolysers. Electrochim. Acta 176, 763–776 (2015).
Tian, Y., Yu, L., Zhuang, C., Zhang, G. & Sun, S. Fast synthesis of Pt single-atom catalyst with high intrinsic activity for hydrogen evolution reaction by plasma sputtering. Mater. Today Energy 22, 100877 (2021).
Li, Y. et al. Tungsten oxide/reduced graphene oxide aerogel with low-content platinum as high-performance electrocatalyst for hydrogen evolution reaction. Small 17, 2102159 (2021).
Lu, F. et al. Engineering platinum-oxygen dual catalytic sites via charge transfer towards highly efficient hydrogen evolution. Angew. Chem. Int. Ed 59, 17712–17718 (2020).
Ye, S. et al. Highly stable single Pt atomic sites anchored on aniline-stacked graphene for hydrogen evolution reaction. Energy Environ. Sci. 12, 1000–1007 (2019).
Cheng, N. et al. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction. Nat. Commun. 7, 13638 (2016).
Kucernak, A. R. & Zalitis, C. General models for the electrochemical hydrogen oxidation and hydrogen evolution reactions: theoretical derivation and experimental results under near mass-transport free conditions. J. Phys. Chem. C 120, 10721–10745 (2016).
Durst, J., Simon, C., Hasché, F. & Gasteiger, H. A. Hydrogen oxidation and evolution reaction kinetics on carbon supported Pt, Ir, Rh, and Pd electrocatalysts in acidic media. J. Electrochem. Soc. 162, F190–F203 (2015).
Nørskov, J. K. et al. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23–J26 (2005).
Esparbé, I. et al. Structure and electrocatalytic performance of carbon-supported platinum nanoparticles. J. Power Sources 190, 201–209 (2009).
Jiang, B., Liao, F., Sun, Y., Cheng, Y. & Shao, M. Pt nanocrystals on nitrogen-doped graphene for the hydrogen evolution reaction using Si nanowires as a sacrificial template. Nanoscale 9, 10138–10144 (2017).
Li, S., Lee, J. K., Zhou, S., Pasta, M. & Warner, J. H. Synthesis of surface grown Pt nanoparticles on edge-enriched MoS2 porous thin films for enhancing electrochemical performance. Chem. Mater. 31, 387–397 (2019).
Durst, J. et al. New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism. Energy Environ. Sci. 7, 2255–2260 (2014).
Neyerlin, K. C., Gu, W., Jorne, J. & Gasteiger, H. A. Study of the exchange current density for the hydrogen oxidation and evolution reactions. J. Electrochem. Soc. 154, B631–B635 (2007).
Hinnemann, B. et al. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J. Am. Chem. Soc. 127, 5308–5309 (2005).
Koch, C. T. Determination of Core Structure Periodicity and Point Defect Density Along Dislocations. PhD thesis, Arizona State Univ. (2002).
Du, Y. et al. XAFCA: a new XAFS beamline for catalysis research. J. Synchrotron Radiat. 22, 839–843 (2015).
Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).
Bunău, O. & Joly, Y. Self-consistent aspects of X-ray absorption calculations. J. Phys. Condens. Matter 21, 345501 (2009).
Lin, X., Zalitis, C. M., Sharman, J. & Kucernak, A. Electrocatalyst performance at the gas/electrolyte interface under high-mass-transport conditions: optimization of the “floating electrode” method. ACS Appl. Mater. Interfaces 12, 47467–47481 (2020).
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
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).
Hammer, B., Hansen, L. B. & Nørskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals. Phys. Rev. B 59, 7413–7421 (1999).
Acknowledgements
H.Z. thanks the NSFC (project 52131301), the Science Technology and Innovation Committee of Shenzhen Municipality (grant SGDX2020110309300301, ‘Preparation of single atoms on transition metal chalcogenides for electrolytic hydrogen evolution’, CityU), the Research Grants Council of Hong Kong (grant AoE/P-701/20 and GRF Project 11315722), ITC via the Hong Kong Branch of the National Precious Metals Material Engineering Research Centre, the Start-Up Grant (project 9380100) and the City University of Hong Kong (projects 9678272, 9680314, 7020054 and 1886921) for support. X.Z. acknowledges support from Hong Kong Polytechnic University (the Start-Up Fund (BDC2) and the Research Institute for Advanced Manufacturing Fund (CD4D)).
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H.Z. proposed the research direction and supervised the project. Z.S. and X.Z. designed and performed the experiments. Z.S., X.L. and G.L. carried out the electrochemical experiments. A.R.J.K. developed the model to fit the electrochemical data. C.L. performed the density functional theory calculation. S.X. performed X-ray absorption experiments and data analysis. B.C. performed the scanning transmission electron microscopy characterization. Z.S. and G.-H.N. carried out the Raman measurement. J.L., Z.G. and C.-S.L. conducted the X-ray photoelectron spectroscopy measurement. Z.S., X.Z. and H.Z. analysed and discussed all experimental results and drafted the manuscript. X.R., L.Z., L.L., Z. Li and X.W. performed some supporting experiments. X.L., G.L., Y.G., C.T., Z. Lai, Z.H., Q.H. and A.R.J.K. helped to write the manuscript. All authors checked the manuscript and agreed with its content.
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Extended data figures and tables
Extended Data Fig. 1 Characterization of the obtained 2H-MoS2 NSs.
a, Scanning electron microscopy image of the exfoliated 2H-MoS2 NSs. b, TEM and c, high-resolution TEM images of a representative 2H-MoS2 NS. Inset in b shows the corresponding SAED pattern. The measured lattice spacing of 2.71 Å in c can be assigned to the {100} planes of the 2H-MoS2 NSs, which is consistent with the theoretical structure of 2H-MoS2 as shown in Supplementary Fig. 4b. d, EDS spectrum and the corresponding element percentages (inset in d) of the 2H-MoS2 NSs showing an expected Mo/S ratio of approximately 1:2. e, AFM image and the measured thicknesses (insets in c) of 2H-MoS2 NSs. f, Thickness distribution histogram of 2H-MoS2 NSs measured by AFM (1.9 nm is the mean thickness and 0.4 nm is the s.d.).
Extended Data Fig. 2 Characterizations of PtNPs/2H-MoS2.
a, TEM image of PtNPs/2H-MoS2. Inset: the diameter distribution histogram of PtNPs grown on 2H-MoS2 NSs (1.1 nm is the mean size and 0.4 nm is the s.d.). b, SAED pattern of PtNPs/2H-MoS2 showing two sets of diffraction spots, which can be assigned to the {111} planes of face-centred cubic (fcc) Pt and the {100} planes of 2H-MoS2. The diffraction spots of Pt align well with those of 2H-MoS2. c, HAADF-STEM image of PtNPs/2H-MoS2. d, The corresponding line scan intensity profiles obtained from the area i and ii in c, respectively. The (111) facets of PtNPs can be observed in c with an average lattice spacing of 2.28 Å as shown in d, which are well aligned with the (100) planes of 2H-MoS2 with a measured lattice spacing of 2.77 Å. These results demonstrated that the ultra-small PtNPs are epitaxially grown on the 2H-MoS2 NSs.
Extended Data Fig. 3 Characterizations of s-Pt-4/1T′-MoS2.
a-d, HAADF-STEM image (a), EDS mapping (b), Raman spectrum (c), and Mo 3d XPS spectrum (d) of the s-Pt-4/1T′-MoS2. Inset in a: the corresponding fast Fourier transform (FFT) pattern of s-Pt-4/1T′-MoS2.
Extended Data Fig. 4 Characterizations of s-Pt-6/1T′-MoS2.
a-d, HAADF-STEM image (a), EDS mapping (b), Raman spectrum (c), and Mo 3d XPS spectrum (d) of the s-Pt-6/1T′-MoS2. Inset in a: the corresponding FFT pattern of s-Pt-6/1T′-MoS2.
Extended Data Fig. 5 Characterizations of PtNPs-12/1T′-MoS2.
a-d, HAADF-STEM image (a), EDS mapping (b), Raman spectrum (c), and Mo 3d XPS spectrum (d) of the PtNPs-12/1T′-MoS2. Inset in a: the corresponding FFT pattern of PtNPs-12/1T′-MoS2.
Extended Data Fig. 6 Characterizations of PtNPs-15/1T′-MoS2.
a-d, HAADF-STEM image (a), EDS mapping (b), Raman spectrum (c), and Mo 3d XPS spectrum (d) of the PtNPs-15/1T′-MoS2. Inset in a: the corresponding FFT pattern of PtNPs-15/1T′-MoS2.
Extended Data Fig. 7 XPS characterizations of Pt with different loading amounts grown on 1T′-MoS2 NSs.
The Pt 4f XPS spectra of s-Pt-4/1T′-MoS2, s-Pt-6/1T′-MoS2, s-Pt/1T′-MoS2, PtNPs-12/1T′-MoS2, and PtNPs-15/1T′-MoS2.
Extended Data Fig. 8 Structural characterizations of s-Pt/1T′-MoS2 before and after the durability test by XAFS.
a, Pt L3-edge XANES, b, Fourier-transformed EXAFS spectra in k space, and c, Fourier-transformed EXAFS spectra in R space of the s-Pt/1T′-MoS2 before and after the durability test. The XANES and EXAFS data exhibit no obvious difference after the durability test indicating that the Pt in the s-Pt/1T′-MoS2 maintains the single-atomically dispersed nature.
Extended Data Fig. 9 HAADF-STEM characterizations of 1T′-MoS2 after the durability test.
a, Atomic-resolution HAADF-STEM image of s-Pt/1T′-MoS2 after the durability test. Inset: the corresponding FFT pattern. b-d, Simulated atomic structures (b1-d1), the corresponding simulated STEM images (b2-d2), and the intensity profiles (b3-d3) of Ptsub (b), Ptads-S (c), and Ptads-Mo (d), respectively. The yellow, blue, and red balls in b1-d1 represent the S, Mo, and Pt atoms, respectively. The dashed curves of the simulated intensity profiles in b3-d3 are taken from the corresponding white dotted rectangles in the simulated STEM images (b2-d2). The histograms of the experimental intensity profiles in b3-d3 are taken from the corresponding white dotted rectangles in a. After the durability test, three kinds of s-Pt, i.e., Ptsub, Ptads-S, and Ptads-Mo, can still be identified on 1T′-MoS2. The experimental intensity profiles (histograms in b3-d3) show good agreement as compared with the simulation results (dashed curves in b3-d3). Several other representative Ptads-S and Ptads-Mo atoms are also marked by the white dotted circles in a. In addition, the 1T′-MoS2 templates showed no phase change after the durability test as confirmed by the HAADT-STEM (a) and the corresponding FFT pattern (inset in a).
Extended Data Fig. 10 DFT calculation results of s-Pt/1T′-MoS2 for HER.
a-c, DFT models of isolated Ptads-S (a), isolated Ptads-Mo (b), and Ptsub+Ptads-S+Ptads-Mo (c) used for the ∆GH and the projected density of states (PDOS) calculation. \({\text{Pt}}_{\text{ads} \mbox{-} \text{S}}^{{\prime} }\), and \({\text{Pt}}_{\text{ads} \mbox{-} \text{Mo}}^{{\prime} }\) in c refer to the Ptads-S and Ptads-Mo in the model of Ptsub+Ptads-S+Ptads-Mo, respectively. The model Ptsub+Ptads-S+Ptads-Mo is established based on the experimental and simulation results shown in Supplementary Fig. 13. The yellow, blue, and red balls in a-c represent the S, Mo, and Pt atoms, respectively. d, Calculated ∆GH diagrams for HER. e, PDOS of the d-band of Pt atoms with the corresponding configurations as shown in a-c. The εd values are shown in e. The black dotted line in e indicates the Fermi level. The εd values of isolated Ptads-S (−2.62 eV) and isolated Ptads-Mo (−2.58 eV) on 1T′-MoS2 are much lower than that of Pt(111) (−1.86 eV). In addition, the εd values of \({\text{Pt}}_{\text{ads} \mbox{-} \text{S}}^{{\prime} }\) and \({\text{Pt}}_{\text{ads} \mbox{-} \text{Mo}}^{{\prime} }\) further shift to −2.78 eV and −2.75 eV, respectively, which are lower than that of isolated Ptads-S and Ptads-Mo, respectively. These results reveal that the hydrogen adsorptions of \({\text{Pt}}_{\text{ads} \mbox{-} \text{S}}^{{\prime} }\) and \({\text{Pt}}_{\text{ads} \mbox{-} \text{Mo}}^{{\prime} }\) are further weakened, resulting in the more positive ∆GH shown in d.
Supplementary information
Supplementary Information
This file contains Supplementary Figs. 1–25, References and Tables 1–7.
Supplementary Video 1
Hydrogen evolution of s-Pt/1T′-MoS2 at 1,500 mA cm−2 in an H-type cell. The video shows the continuous bubbles being produced and released from the surface of the s-Pt/1T′-MoS2 electrode (Pt loading: 0.0175 mg cm−2) during the electrocatalytic hydrogen evolution at 1,500 mA cm−2 in an H-type cell.
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Shi, Z., Zhang, X., Lin, X. et al. Phase-dependent growth of Pt on MoS2 for highly efficient H2 evolution. Nature 621, 300–305 (2023). https://doi.org/10.1038/s41586-023-06339-3
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DOI: https://doi.org/10.1038/s41586-023-06339-3
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