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High-metallic-phase-concentration Mo1–xWxS2 nanosheets with expanded interlayers as efficient electrocatalysts

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Abstract

In most cases, layered transition metal dichalcogenides (LTMDs), containing metallic phases, show electrochemical behavior different from their semiconductor counterparts. Typically, two-dimensional layered metallic 1T-MoS2 demonstrates better electrocatalytic performance for water splitting compared to its 2H counterpart. However, the characteristics of low metallic phase concentration and poor stability limit its applications in some cases. Herein, we demonstrate a simple and efficient bottom-up wet-chemistry strategy for the large-scale synthesis of nanoscopic ultrathin Mo1–xWxS2 nanosheets with enlarged interlayer spacing and high metallic phase concentration. Our characterizations, including X-ray absorption fine structure spectroscopy (XAFS), high-angle annular dark-fieldscanning transmission electron microscopy (HAADF-STEM), and X-ray photoelectron spectroscopy (XPS) revealed that the metallic ultrathin ternary Mo1–xWxS2 nanosheets exhibited distorted metal–metal bonds and a tunable metallic phase concentration. As a proof of concept, this optimized catalyst, with the highest metallic phase concentration (greater than 90%), achieved a low overpotential of about–155 mV at a current density of –10 mA/cm2, a small Tafel slope of 67 mV/dec, and an increased turnover frequency (TOF) of 1.3 H2 per second at an overpotential of –300 mV (vs. reversible hydrogen electrode (RHE)), highlighting the importance of the metallic phase. More importantly, this study can lead to a facile solvothermal route to prepare stable and high-metallicphase-concentration transition-metal-based two-dimensional materials for future applications.

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References

  1. Karunadasa, H. I.; Chang, C. J.; Long, J. R. A molecular molybdenum-oxo catalyst for generating hydrogen from water. Nature 2010, 464, 1329–1333.

    Article  Google Scholar 

  2. Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; Mi, Q. X.; Santori, E. A.; Lewis, N. S. Solar water splitting cells. Chem. Rev. 2010, 110, 6446–6471.

    Article  Google Scholar 

  3. Dresselhaus, M. S.; Thomas, I. L. Alternative energy technologies. Nature 2001, 414, 332–337.

    Article  Google Scholar 

  4. Turner, J. A. Sustainable hydrogen production. Science 2004, 305, 972–974.

    Article  Google Scholar 

  5. Zhao, Y.; Kamiya, K.; Hashimoto, K.; Nakanishi, S. In situ CO2-emission assisted synthesis of molybdenum carbonitride nanomaterial as hydrogen evolution electrocatalyst. J. Am. Chem. Soc. 2015, 137, 110–113.

    Article  Google Scholar 

  6. Zheng, Y.; Jiao, Y.; Zhu, Y. H.; Li, L. H.; Han, Y.; Chen, Y.; Du, A. J.; Jaroniec, M.; Qiao, S. Z. Hydrogen evolution by a metal-free electrocatalyst. Nat. Commun. 2014, 5, 3783.

    Article  Google Scholar 

  7. Stamenkovic, V. R.; Mun, B. S.; Arenz, M.; Mayrhofer, K. J. J.; Lucas, C. A.; Wang, G. F.; Ross, P. N.; Markovic, N. M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat. Mater. 2007, 6, 241–247.

    Article  Google Scholar 

  8. Dempsey, J. L.; Brunschwig, B. S.; Winkler, J. R.; Gray, H. B. Hydrogen evolution catalyzed by cobaloximes. Acc. Chem. Res. 2009, 42, 1995–2004.

    Article  Google Scholar 

  9. Xie, J. F.; Zhang, J. J.; Li, S.; Grote, F. B.; Zhang, X. D.; Zhang, H.; Wang, R. X.; Lei, Y.; Pan, B. C.; Xie, Y. Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution. J. Am. Chem. Soc. 2013, 135, 17881–17888.

    Article  Google Scholar 

  10. Xing, Z. C.; Yang, X. R.; Asiri, A. M.; Sun, X. P. Threedimensional structures of MoS2@Ni core/shell nanosheets array toward synergetic electrocatalytic water splitting. ACS Appl. Mater. Interface 2016, 8, 14521–14526.

    Article  Google Scholar 

  11. Kong, D. S.; Wang, H. T.; Lu, Z. Y.; Cui, Y. CoSe2 nanoparticles grown on carbon fiber paper: An efficient and stable electrocatalyst for hydrogen evolution reaction. J. Am. Chem. Soc. 2014, 136, 4897–4900.

    Article  Google Scholar 

  12. Faber, M. S.; Jin, S. Earth-abundant inorganic electrocatalysts and their nanostructures for energy conversion applications. Energy Environ. Sci. 2014, 7, 3519–3542.

    Article  Google Scholar 

  13. Li, Y. H.; Liu, P. F.; Pan, L. F.; Wang, H. F.; Yang, Z. Z.; Zheng, L. R.; Hu, P.; Zhao, H. J.; Gu, L.; Yang, H. G. Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water. Nat. Commun. 2015, 6, 8064.

    Article  Google Scholar 

  14. Popczun, E. J.; McKone, J. R.; Read, C. G.; Biacchi, A. J.; Wiltrout, A. M.; Lewis, N. S.; Schaak, R. E. Nanostructured nickel phosphide as an electrocatalyst for the hydrogen evolution reaction. J. Am. Chem. Soc. 2013, 135, 9267–9270.

    Article  Google Scholar 

  15. Vrubel, H.; Hu, X. L. Molybdenum boride and carbide catalyze hydrogen evolution in both acidic and basic solutions. Angew. Chem., Int. Ed. 2012, 124, 12875–12878.

    Article  Google Scholar 

  16. Peng, S. J.; Li, L. L.; Han, X. P.; Sun, W. P.; Srinivasan, M.; Mhaisalkar, S. G.; Cheng, F. Y.; Yan, Q. Y.; Chen, J.; Ramakrishna, S. Cobalt sulfide nanosheet/graphene/carbon nanotube nanocomposites as flexible electrodes for hydrogen evolution. Angew. Chem., Int. Ed. 2014, 126, 12802–12807.

    Article  Google Scholar 

  17. Voiry, D.; Yamaguchi, H.; Li, J. W.; Silva, R.; Alves, D. C. B.; Fujita, T.; Chen, M. W.; Asefa, T.; Shenoy, V. B.; Eda, G. et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat. Mater. 2013, 12, 850–855.

    Article  Google Scholar 

  18. Ye, R. Q.; del Angel-Vicente, P.; Liu, Y. Y.; Arellano- Jimenez, M. J.; Peng, Z. W.; Wang, T.; Li, Y. L.; Yakobson, B. I.; Wei, S. H.; Yacaman, M. J. et al. High-performance hydrogen evolution from MoS2(1–x)Px solid solution. Adv. Mat. 2016, 28, 1427–1432.

    Article  Google Scholar 

  19. Chhowalla, M.; Shin, H. S.; Eda, G.; Li, L. J.; Loh, K. P.; Zhang, H. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 2013, 5, 263–275.

    Article  Google Scholar 

  20. Zeng, Z. Y.; Tan, C. L.; Huang, X.; Bao, S. Y.; Zhang, H. Growth of noble metal nanoparticles on single-layer TiS2 and TaS2 nanosheets for hydrogen evolution reaction. Energy Environ. Sci. 2014, 7, 797–803.

    Article  Google Scholar 

  21. Tan, C. L.; Zhang, H. Two-dimensional transition metal dichalcogenide nanosheet-based composites. Chem. Soc. Rev. 2015, 44, 2713–2731.

    Article  Google Scholar 

  22. Merki, D.; Fierro, S.; Vrubel, H.; Hu, X. L. Amorphous molybdenum sulfide films as catalysts for electrochemical hydrogen production in water. Chem. Sci. 2011, 2, 1262–1267.

    Article  Google Scholar 

  23. Voiry, D.; Yang, J.; Chhowalla, M. Recent strategies for improving the catalytic activity of 2D TMD nanosheets toward the hydrogen evolution reaction. Adv. Mater. 2016, 28, 6197–6206.

    Article  Google Scholar 

  24. Yu, Y. F.; Huang, S. Y.; Li, Y. P.; Steinmann, S. N.; Yang, W. T.; Cao, L. Y. Layer-dependent electrocatalysis of MoS2 for hydrogen evolution. Nano Lett. 2014, 14, 553–558.

    Article  Google Scholar 

  25. Zhao, X.; Ma, X.; Sun, J.; Li, D. H.; Yang, X. R. Enhanced catalytic activities of surfactant-assisted exfoliated WS2 nanodots for hydrogen evolution. ACS Nano 2016, 10, 2159–2166.

    Article  Google Scholar 

  26. Merki, D.; Hu, X. L. Recent developments of molybdeuum and tungsten sulfides as hydrogen evolution catalysts. Energy Environ. Sci. 2011, 4, 3878–3888.

    Article  Google Scholar 

  27. He, J. N.; Liang, Y. Q.; Mao, J.; Zhang, X. M.; Yang, X. J.; Cui, Z. D.; Zhu, S. L.; Li, Z. Y.; Li, B. B. 3D tungsten-doped MoS2 nanostructure: A low-cost, facile prepared catalyst for hydrogen evolution reaction. J. Electrochem. Soc. 2016, 163, H299–H304.

    Article  Google Scholar 

  28. Wang, L.; Sofer, Z.; Luxa, J.; Pumere, M. MoxW1–xS2 solid solutions as 3D electrodes for hydrogen evolution reaction. Adv. Mater. Interfaces 2015, 2, 1500041.

    Article  Google Scholar 

  29. Zhang, X. W.; Meng, F.; Mao, S.; Ding, Q.; Shearer, M. J.; Faber, M. S.; Chen, J. H.; Hamers, R. J.; Jin, S. Amorphous MoSxCly electrocatalysts supported by vertical graphene for efficient electrochemical and photoelectrocemical hydrogen generation. Energy Environ. Sci. 2015, 8, 862–868.

    Article  Google Scholar 

  30. Fu, Q.; Yang, L.; Wang, W. H.; Han, A. L.; Huang, J.; Du, P. W.; Fan, Z. Y.; Zhang, J. Y.; Xiang, B. Synthesis and enhanced electrochemical catalytic performance of monolayer WS2(1–x)Se2x with a tunable band gap. Adv. Mater. 2015, 27, 4732–4738.

    Article  Google Scholar 

  31. Gong, Q. F.; Cheng, L.; Liu, C. H.; Zhang, M.; Feng, Q. L.; Ye, H. L.; Zeng, M.; Xie, L. M.; Liu, Z.; Li, Y. G. Ultrathin MoS2(1–x)Se2x alloy nanoflakes for electrocatalytic hydrogen evolution reaction. ACS Catal. 2015, 5, 2213–2219.

    Article  Google Scholar 

  32. Kibsgaard, J.; Chen, Z. B.; Reinecke, B. N.; Jaramillo, T. F. Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat. Mater. 2012, 11, 963–969.

    Article  Google Scholar 

  33. Cai, Y.; Yang, X.; Liang, T.; Dai, L.; Ma, L.; Huang, G. W.; Chen, W. X.; Chen, H. Z.; Su, H. X.; Xu, M. S. Easy incorporation of single-walled carbon nanotubes into twodimensional MoS2 for high-performance hydrogen evolution. Nanotechnology 2014, 25, 465401.

    Article  Google Scholar 

  34. Duan, J. J.; Chen, S.; Chambers, B. A.; Andersson, G. G.; Qiao, S. Z. 3D WS2 nanolayers@heteroatom-doped graphene films as hydrogen evolution catalyst electrodes. Adv. Mater. 2015, 27, 4234–4241.

    Article  Google Scholar 

  35. Wypych, F.; Solenthaler, C.; Prins, R.; Weber, Th. Electron diffraction study of intercalation compounds derived from 1T-MoS2. J. Solid State Chem. 1999, 144, 430–436.

    Article  Google Scholar 

  36. Lukowski, M. A.; Daniel, A. S.; English, C. R.; Meng, F.; Forticaux, A.; Hamers, R. J.; Jin, S. Highly active hydrogen evolution catalysis from metallic WS2 nanosheets. Energy Environ. Sci. 2014, 7, 2608–2613.

    Article  Google Scholar 

  37. Lukowski, M. A.; Daniel, A. S.; Meng, F.; Forticaux, A.; Li, L. S.; Jin, S. Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS2 nanosheets. J. Am. Chem. Soc. 2013, 135, 10274–10277.

    Article  Google Scholar 

  38. Voiry, D.; Salehi, M.; Silva, R.; Fujita, T.; Chen, M. W.; Asefa, T.; Shenoy, V. B.; Eda, G.; Chhowalla, M. Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Lett. 2013, 13, 6222–6227.

    Article  Google Scholar 

  39. Wypych, F.; Schöllhorn, R. 1T-MoS2, a new metallic modification of molybdenum disulfide. J. Chem. Soc. Chem. Commun. 1992, 1386–1388.

    Google Scholar 

  40. Liu, Q.; Li, X. L.; Xiao, Z. R.; Zhou, Y.; Chen, H. P.; Khalil, A.; Xiang, T.; Xu, J. Q.; Chu, W. S.; Wu, X. J. et al. Stable metallic 1T-WS2 nanoribbons intercalated with ammonia ions: The correlation between structure and electrical/optical properties. Adv. Mater. 2015, 27, 4837–4844.

    Article  Google Scholar 

  41. Liu, Q.; Li, X. L.; He, Q.; Khalil, A.; Liu, D. B.; Xiang, T.; Wu, X. J.; Song, L. Gram-scale aqueous synthesis of stable few-layered 1T-MoS2: Applications for visible-light-driven photocatalytic hydrogen evolution. Small 2015, 11, 5556–5564.

    Article  Google Scholar 

  42. Liu, Q.; Sun, C. Y.; He, Q.; Khalil, A.; Xiang, T.; Liu, D. B.; Zhou, Y.; Wang, J.; Song, L. Stable metallic 1T-WS2 ultrathin nanosheets as a promising agent for near-infrared photothermal ablation cancer therapy. Nano Res. 2015, 8, 3982–3991.

    Article  Google Scholar 

  43. Wang, F. M.; Li, J. S.; Wang, F.; Shifa, T. A.; Cheng, Z. Z.; Wang, Z. X.; Xu, K.; Zhan, X. Y.; Wang, Q. S.; Huang, Y. et al. Enhanced electrochemical H2 evolution by few-layered metallic WS2(1–x)Se2x nanoribbons. Adv. Funct. Mater. 2015, 25, 6077–6083.

    Article  Google Scholar 

  44. Ressler, T. WinXAS: A program for X-ray absorption spectroscopy data analysis under MS-windows. J. Synchrotron Rad. 1998, 5, 118–122.

    Article  Google Scholar 

  45. Ankudinov, A. L.; Ravel, B.; Rehr, J. J.; Conradson, S. D. Real-space multiple-scattering calculation and interpretation of X-ray absorption near-edge structure. Phys. Rev. B 1998, 58, 7565–7576.

    Article  Google Scholar 

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

    Article  Google Scholar 

  47. Mortensen; J. J.; Hansen, L. B.; Jacobsen, K. W. Real-space grid implementation of the projector augmented wave method. Phys. Rev. B 2005, 71, 035109.

    Article  Google Scholar 

  48. Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.

    Article  Google Scholar 

  49. Monkhorst, H. J.; Pack, J. D. Special points for Brillouinzone integrations. Phys. Rev. B 1976, 13, 5188–5192.

    Article  Google Scholar 

  50. Fan, X. L.; Wang, S. Y.; An, Y. R.; Lau, W. Catalytic activity of MS2 monolayer for electrochemical hydrogen evolution. J. Phys. Chem. C 2016, 120, 1623–1632.

    Article  Google Scholar 

  51. Chou, S. S.; Sai, N.; Lu, P.; Coker, E. N.; Liu, S.; Artyushkova, K.; Luk, T. S.; Kaehr, B.; Brinker, C. J. Understanding catalysis in a multiphasic two-dimensional transition metal dichalcogenide. Nat. Commun. 2015, 6, 8311.

    Article  Google Scholar 

  52. Nørskov, J. K.; Bligaard, T.; Logadottir, A.; Kitchin, J. R.; Chen, J. G.; Pandelov, S.; Stimming, U. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 2005, 152, J23–J26.

    Article  Google Scholar 

  53. Faber, M. S.; Dziedzic, R.; Lukowski, M. A.; Kaiser, N. S.; Ding, Q.; Jin, S. High-performance electrocatalysis using metallic cobalt pyrite (CoS2) micro- and nanostructures. J. Am. Chem. Soc. 2014, 136, 10053–10061.

    Article  Google Scholar 

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Acknowledgements

We acknowledge the financial support of the National Basic Research Program of China (Nos. 2014CB848900 and 2016YFA0200602), the National Natural Science Foundation of China (Nos. U1532112, 11375198, 11574280, and 21573204), CUSF (No. WK2310000053) and funds from Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education). L. S. thanks the recruitment program of global experts, the CAS Hundred Talent Program. We also thank the Shanghai synchrotron Radiation Facility (14W1, SSRF), the Beijing Synchrotron Radiation Facility (1W1B and soft-X-ray endstation, BSRF), the Hefei Synchrotron Radiation Facility (MCD and Photoemission Endstations, NSRL) and USTC Center for Micro and Nanoscale Research and Fabrication.

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  1. Qun He, Yangyang Wan and Hongliang Jiang contributed equally to this work.

Authors and Affiliations

  1. National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, 230029, China

    Qun He, Hongliang Jiang, Chuanqiang Wu, Shuangming Chen, Yu Zhou, Haiping Chen, Daobin Liu, Yasir A. Haleem & Li Song

  2. CAS Key Lab of Materials for Energy Conversion, CAS Center for Excellence in Nanoscience, Hefei National Laboratory for Physical Science at the Microscale, Synergetic Innovation of Quantum Information & Quantum Technology, University of Science and Technology of China, Hefei, 230026, China

    Yangyang Wan, Zhongti Sun & Xiaojun Wu

  3. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, China

    Binghui Ge

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  1. Qun He
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Correspondence to Shuangming Chen, Xiaojun Wu or Li Song.

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He, Q., Wan, Y., Jiang, H. et al. High-metallic-phase-concentration Mo1–xWxS2 nanosheets with expanded interlayers as efficient electrocatalysts. Nano Res. 11, 1687–1698 (2018). https://doi.org/10.1007/s12274-017-1786-x

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