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Journal of Sol-Gel Science and Technology

, Volume 88, Issue 1, pp 227–235 | Cite as

Synthesis of amorphous MoSx and MoSx/carbon nanotubes composite aerogels as effective hydrogen evolution reaction catalysts

  • Qiuyue Gao
  • Yani Jin
  • Yiming Jin
  • Xiaoqing Wang
  • Ziran Ye
  • Zhanglian Hong
  • Mingjia Zhi
Original Paper: Sol–gel and hybrid materials for catalytic, photoelectrochemical, and sensor applications

Abstract

This work reported the preparation of amorphous MoSx aerogel and MoSx/carbon nanotubes composite aerogels by a modified epoxide addition sol–gel method. In this process, propylene epoxide scavenged the protons from a S–H-contained organic acid (dl-Mercaptosuccinic acid) and promoted the interactions between (NH4)6Mo7O24•4H2O and the functional groups in the organic acid to form a gel. The sulfur and molybdenum contained a wet gel turned into an amorphous MoSx aerogel after supercritical drying in ethanol. Carbon nanotubes can be further incorporated into the aerogel backbone, which can extend the specific surface area and alter the pore structures in the composite aerogels. Such composite aerogels showed good catalytic performance in electrochemical hydrogen evolution reactions.

MoSx aerogels can be prepared by the modified epoxide-adding method and showed good catalytic activity toward HER.

Highlights

  • Epoxide addition method has been adopted to synthesize amorphous molybdenum sulfide aerogel.

  • High surface area (up to 265.5 m2/g) and the developed pore structure (pore volume up to 0.89 cm3/g) have been achieved.

  • Low overpotential and high activity toward hydrogen evolution have been observed.

Keywords

Sol–gel Molybdenum sulfide Carbon nanotubes Aerogel Hydrogen evolution reaction 

Notes

Acknowledgements

This work is supported by the National Key Research and Development program (grant no. 2016YFB0901600) and NSCF (grant no. 21303162 and grant no. 11604295).

Conflict of interest

The authors declare that they have no conflict of interest.

Ethical statement

I certify that this paper is original and has not been published and will not be submitted elsewhere for publication while being considered by Journal of Sol–Gel Science and Technology. And the study is not split up into several parts to increase the quantity of submissions and submitted to various journals or to one journal over time. No data have been fabricated or manipulated (including images) to support our conclusions. No data, text, or theories by others are presented as if they were the authors’ own. The submission has been received explicitly from all co-authors. And authors whose names appear on the submission have contributed sufficiently to the scientific work and therefore share collective responsibility and accountability for the results.

References

  1. 1.
    Li Y, Wang H, Xie L, Liang Y, Hong G, Dai H (2011) MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. J Am Chem Soc 133(19):7296–7299.  https://doi.org/10.1021/ja201269b CrossRefGoogle Scholar
  2. 2.
    Meng FK, Li JT, Cushing SK, Zhi MJ, Wu NQ (2013) Solar hydrogen generation by nanoscale p-n junction of p-type molybdenum disulfide/n-type nitrogen-doped reduced graphene oxide. J Am Chem Soc 135(28):10286–10289.  https://doi.org/10.1021/ja404851s CrossRefGoogle Scholar
  3. 3.
    An Y-R, Fan X-L, Luo Z-F, Lau W-M (2017) Nanopolygons of monolayer MS2: best morphology and size for HER catalysis. Nano Lett 17(1):368–376.  https://doi.org/10.1021/acs.nanolett.6b04324 CrossRefGoogle Scholar
  4. 4.
    Jaramillo TF, Jørgensen KP, Bonde J, Nielsen JH, Horch S, Chorkendorff I (2007) Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317(5834):100–102.  https://doi.org/10.1126/science.1141483 CrossRefGoogle Scholar
  5. 5.
    Hinnemann B, Moses PG, Bonde J, Jørgensen KP, Nielsen JH, Horch S, Chorkendorff I, Nørskov JK (2005) Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J Am Chem Soc 127(15):5308–5309.  https://doi.org/10.1021/ja0504690 CrossRefGoogle Scholar
  6. 6.
    Xie J, Zhang J, Li S, Grote F, Zhang X, Zhang H, Wang R, Lei Y, Pan B, Xie Y (2013) Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution. J Am Chem Soc 135(47):17881–17888.  https://doi.org/10.1021/ja408329q CrossRefGoogle Scholar
  7. 7.
    Lai C, Zhou Z, Zhang L, Wang X, Zhou Q, Zhao Y, Wang Y, Wu X-F, Zhu Z, Fong H (2014) Free-standing and mechanically flexible mats consisting of electrospun carbon nanofibers made from a natural product of alkali lignin as binder-free electrodes for high-performance supercapacitors. J Power Sources 247:134–141.  https://doi.org/10.1016/j.jpowsour.2013.08.082 CrossRefGoogle Scholar
  8. 8.
    Park HS, Han SB, Kwak DH, Lee GH, Choi IA, Kim DH, Ma KB, Kim MC, Kwon HJ, Park KW (2017) Sulfur‐doped porphyrinic carbon nanostructures synthesized with amorphous MoS2 for the oxygen reduction reaction in an acidic medium. ChemSusChem 10(10):2202–2209.  https://doi.org/10.1002/cssc.201700147 CrossRefGoogle Scholar
  9. 9.
    Zhao Y, Xie X, Zhang J, Liu H, Ahn H-J, Sun K, Wang G (2015) MoS2 nanosheets supported on 3D graphene aerogel as a highly efficient catalyst for hydrogen evolution. Chem – A Eur J 21(45):15908–15913.  https://doi.org/10.1002/chem.201501964 CrossRefGoogle Scholar
  10. 10.
    Qi Y, Xu Q, Wang Y, Yan B, Ren Y, Chen Z (2016) CO2-induced phase engineering: protocol for enhanced photoelectrocatalytic performance of 2D MoS2 nanosheets. ACS Nano 10(2):2903–2909.  https://doi.org/10.1021/acsnano.6b00001 CrossRefGoogle Scholar
  11. 11.
    Worsley MA, Shin SJ, Merrill MD, Lenhardt J, Nelson AJ, Woo LY, Gash AE, Baumann TF, Orme CA (2015) Ultralow density, monolithic WS2, MoS2, and MoS2/graphene aerogels. ACS Nano 9(5):4698–4705.  https://doi.org/10.1021/acsnano.5b00087 CrossRefGoogle Scholar
  12. 12.
    Long H, Harley-Trochimczyk A, Pham T, Tang Z, Shi T, Zettl A, Carraro C, Worsley MA, Maboudian R (2016) High surface area MoS2/graphene hybrid aerogel for ultrasensitive NO2 detection. Adv Funct Mater 26(28):5158–5165.  https://doi.org/10.1002/adfm.201601562 CrossRefGoogle Scholar
  13. 13.
    Long H, Chan L, Harley-Trochimczyk A, Luna LE, Tang Z, Shi T, Zettl A, Carraro C, Worsley MA, Maboudian R (2017) 3D MoS2 aerogel for ultrasensitive NO2 detection and its tunable sensing behavior. Adv Mater Interfaces 4(16):1700217.  https://doi.org/10.1002/admi.201700217 CrossRefGoogle Scholar
  14. 14.
    Li N, Chai Y, Dong B, Liu B, Guo H, Liu C (2012) Preparation of porous MoS2 via a sol–gel route using (NH4)2Mo3S13 as precursor. Mater Lett 88:112–115.  https://doi.org/10.1016/j.matlet.2012.08.031 CrossRefGoogle Scholar
  15. 15.
    Guo X, Wang Z, Zhu W, Yang H (2017) The novel and facile preparation of multilayer MoS2 crystals by a chelation-assisted sol-gel method and their electrochemical performance. RSC Adv 7(15):9009–9014.  https://doi.org/10.1039/C6RA25558B CrossRefGoogle Scholar
  16. 16.
    Guo X, Yin P, Wang Z, Yang H (2018) Template-assisted sol–gel synthesis of porous MoS2/C nanocomposites as anode materials for lithium-ion batteries. J Sol-Gel Sci Technol 85(1):140–148.  https://doi.org/10.1007/s10971-017-4531-8 CrossRefGoogle Scholar
  17. 17.
    Arachchige IU, Armatas GS, Biswas K, Subrahmanyam KS, Latturner S, Malliakas CD, Manos MJ, Oh Y, Polychronopoulou K, P. Poudeu, Trikalitis PF, Zhang PN, Zhao Q, Peter SC L-D (2017) Mercouri G. Kanatzidis: excellence and innovations in inorganic and solid-state chemistry. Inorg Chem 56(14):7582–7597.  https://doi.org/10.1021/acs.inorgchem.7b00933 CrossRefGoogle Scholar
  18. 18.
    Doan-Nguyen VVT, Subrahmanyam KS, Butala MM, Gerbec JA, Islam SM, Kanipe KN, Wilson CE, Balasubramanian M, Wiaderek KM, Borkiewicz OJ, Chapman KW, Chupas PJ, Moskovits M, Dunn BS, Kanatzidis MG, Seshadri R (2016) Molybdenum polysulfide chalcogels as high-capacity, anion-redox-driven electrode materials for Li-ion batteries. Chem Mater 28(22):8357–8365.  https://doi.org/10.1021/acs.chemmater.6b03656 CrossRefGoogle Scholar
  19. 19.
    Subrahmanyam KS, Malliakas CD, Sarma D, Armatas GS, Wu J, Kanatzidis MG (2015) Ion-exchangeable molybdenum sulfide porous chalcogel: gas adsorption and capture of iodine and mercury. J Am Chem Soc 137(43):13943–13948.  https://doi.org/10.1021/jacs.5b09110 CrossRefGoogle Scholar
  20. 20.
    Islam SM, Subrahmanyam KS, Malliakas CD, Kanatzidis MG (2014) One-dimensional molybdenum thiochlorides and their use in high surface area MoSx chalcogels. Chem Mater 26(17):5151–5160.  https://doi.org/10.1021/cm5024579 CrossRefGoogle Scholar
  21. 21.
    Staszak-Jirkovský J, Malliakas Christos D, Lopes Pietro P, Danilovic N, Kota Subrahmanyam S, Chang K-C, Genorio B, Strmcnik D, Stamenkovic Vojislav R, Kanatzidis MG, Markovic NM (2015) Design of active and stable Co–Mo–Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction. Nat Mater 15:197.  https://doi.org/10.1038/nmat4481 CrossRefGoogle Scholar
  22. 22.
    Gao Q, Wang X, Shi Z, Ye Z, Wang W, Zhang N, Hong Z, Zhi M (2018) Synthesis of porous NiCo2S4 aerogel for supercapacitor electrode and oxygen evolution reaction electrocatalyst. Chem Eng J 331:185–193.  https://doi.org/10.1016/j.cej.2017.08.067 CrossRefGoogle Scholar
  23. 23.
    Gao Q, Shi Z, Xue K, Ye Z, Hong Z, Yu X, Zhi M (2018) Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances. Nanotechnology 29(21):215601CrossRefGoogle Scholar
  24. 24.
    Gash AE, Tillotson TM, Satcher JH, Poco JF, Hrubesh LW, Simpson RL (2001) Use of epoxides in the sol−gel synthesis of porous iron (III) oxide monoliths from Fe (III) salts. Chem Mater 13(3):999–1007.  https://doi.org/10.1021/cm0007611 CrossRefGoogle Scholar
  25. 25.
    Klimova TE, Valencia D, Mendoza-Nieto JA, Hernández-Hipólito P (2013) Behavior of NiMo/SBA-15 catalysts prepared with citric acid in simultaneous hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene. J Catal 304:29–46.  https://doi.org/10.1016/j.jcat.2013.03.027 CrossRefGoogle Scholar
  26. 26.
    Du A, Zhou B, Zhong Y, Zhu X, Gao G, Wu G, Zhang Z, Shen J (2011) Hierarchical microstructure and formative mechanism of low-density molybdena-based aerogel derived from MoCl5. J Sol-Gel Sci Technol 58(1):225–231.  https://doi.org/10.1007/s10971-010-2381-8 CrossRefGoogle Scholar
  27. 27.
    Du A, Zhou B, Zhang Z, Shen J (2013) A special material or a new state of matter: a review and reconsideration of the aerogel. Materials 6(3):941–968CrossRefGoogle Scholar
  28. 28.
    Wanger CD, Riggs WM, Davis LE, Moulder JF, Muilenberg GE (1979) Handbook of X ray photoelectron spectroscopy. Perkin‐Elmer Corp, Eden Prairie, Minnesota, USAGoogle Scholar
  29. 29.
    Wang HW, Skeldon P, Thompson GE (1997) XPS studies of MoS2 formation from ammonium tetrathiomolybdate solutions. Surf Coat Technol 91(3):200–207.  https://doi.org/10.1016/S0257-8972(96)03186-6 CrossRefGoogle Scholar
  30. 30.
    Benck JD, Chen Z, Kuritzky LY, Forman AJ, Jaramillo TF (2012) Amorphous molybdenum sulfide catalysts for electrochemical hydrogen production: insights into the origin of their catalytic activity. ACS Catalysis 2(9):1916–1923.  https://doi.org/10.1021/cs300451q CrossRefGoogle Scholar
  31. 31.
    Vrubel H, Moehl T, Gratzel M, Hu X (2013) Revealing and accelerating slow electron transport in amorphous molybdenum sulphide particles for hydrogen evolution reaction. Chem Commun 49(79):8985–8987.  https://doi.org/10.1039/C3CC45416A CrossRefGoogle Scholar
  32. 32.
    Du A, Zhou B, Shen J, Xiao S, Zhang Z, Liu C, Zhang M (2009) Monolithic copper oxide aerogel via dispersed inorganic sol–gel method. J Non-Cryst Solids 355(3):175–181.  https://doi.org/10.1016/j.jnoncrysol.2008.11.015 CrossRefGoogle Scholar
  33. 33.
    Bi Y, Ren H, Chen B, Chen G, Mei Y, Zhang L (2012) Synthesis monolithic copper-based aerogel with polyacrylic acid as template. J Sol-Gel Sci Technol 63(1):140–145.  https://doi.org/10.1007/s10971-012-2777-8 CrossRefGoogle Scholar
  34. 34.
    Kido Y, Nakanishi K, Miyasaka A, Kanamori K (2012) Synthesis of monolithic hierarchically porous iron-based xerogels from iron(III) salts via an epoxide-mediated sol–gel process. Chem Mater 24(11):2071–2077.  https://doi.org/10.1021/cm300495j CrossRefGoogle Scholar
  35. 35.
    Bi YT, Ren HB, Chen BW, Zhang L (2011) Synthesis and characterization of nickel-based monolithic aerogel via sol-gel method. Adv Mater Res 335-336:368–371.  https://doi.org/10.4028/www.scientific.net/AMR.335-336.368 CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.State Key Laboratory of Silicon Materials, School of Materials Science and EngineeringZhejiang UniversityHangzhouChina
  2. 2.Department of Applied PhysicsZhejiang University of TechnologyHangzhouChina

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