Solid-state synthesis of MoS2 nanorod from molybdenum-organic framework for efficient hydrogen evolution reaction

More info
  • ReceivedNov 29, 2018
  • AcceptedJan 7, 2019
  • PublishedJan 24, 2019


Funded by

We acknowledge the financial support from the National Key Research and Development Program of China(2017YFA0700100,2018YFA0208600)

Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)

National Natural Science Foundation of China(21671188,21871263,21331006)

Key Research Program of Frontier Science


Youth Innovation Promotion Association



We acknowledge the financial support from the National Key Research and Development Program of China (2017YFA0700100 and 2018YFA0208600), Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000), National Natural Science Foundation of China (21671188, 21871263 and 21331006), Key Research Program of Frontier Science, CAS (QYZDJ-SSW-SLH045) and Youth Innovation Promotion Association, CAS (2014265).

Interest statement

The authors declare no conflict of interest.

Contributions statement

Cao R and Huang YB conceived and designed the experiments. Yi JD performed the catalyst preparation, characterizations, and wrote the paper. Liu TT helped with the sample characterization. All authors contributed to the general discussion.

Author information

Jun-Dong Yi received his bachelor’s degree from the School of Materials Science and Engineering, Central South University in 2013. Then he received his PhD degree in Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences in 2018. He is currently a postdoctoral research associate in Prof. Rong Cao’s group in FJIRSM. His current research interest focuses on designing high-performance electrocatalysts for water splitting, fuel cells and other energy conversion systems.

Yuan-Biao Huang obtained his PhD degree in 2009 under the supervision of Prof. GX. Jin from Fudan University. He joined Prof. Rong Cao’s group at FJIRSM, Chinese Academy of Sciences in 2009. In 2014, he joined Prof. Qiang Xu’s group at the National Institute of Advanced Industrial Science and Technology as a JSPS (Japan Society for the Promotion of Science) fellow. In 2015, he moved back to Prof. Cao’s research group at FJIRSM. His research interest focuses on porous MOF and covalent organic frameworks (COF) based materials for catalysis.

Rong Cao was born in Fujian province, China. He obtained his PhD degree from FJIRSM, Chinese Academy of Sciences, in 1993. Following post-doctoral experience in Hong Kong Polytechnic University and JSPS Fellowship in Nagoya University, he became a professor at FJIRSM in 1998. Now, he is the director of FJIRSM. His main research interest includes supramolecular chemistry, inorganic-organic hybrid materials and nanocatalysis.


Supplementary information

Supporting data are available in the online version of the paper.


[1] Dresselhaus MS, Thomas IL. Alternative energy technologies. Nature, 2001, 414: 332-337 CrossRef PubMed Google Scholar

[2] Chu S, Majumdar A. Opportunities and challenges for a sustainable energy future. Nature, 2012, 488: 294-303 CrossRef PubMed ADS Google Scholar

[3] Turner JA. Sustainable hydrogen production. Science, 2004, 305: 972-974 CrossRef PubMed ADS Google Scholar

[4] Mallouk TE. Water electrolysis: divide and conquer. Nat Chem, 2013, 5: 362-363 CrossRef PubMed ADS Google Scholar

[5] Zou X, Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting. Chem Soc Rev, 2015, 44: 5148-5180 CrossRef PubMed Google Scholar

[6] Morales-Guio CG, Stern LA, Hu X. Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem Soc Rev, 2014, 43: 6555 CrossRef PubMed Google Scholar

[7] Li P, Yang Z, Shen J, et al. Subnanometer molybdenum sulfide on carbon nanotubes as a highly active and stable electrocatalyst for hydrogen evolution reaction. ACS Appl Mater Interfaces, 2016, 8: 3543-3550 CrossRef Google Scholar

[8] Zhu B, Zou R, Xu Q. Metal-organic framework based catalysts for hydrogen evolution. Adv Energy Mater, 2018, 8: 1801193 CrossRef Google Scholar

[9] Tabassum H, Guo W, Meng W, et al. Metal-organic frameworks derived cobalt phosphide architecture encapsulated into B/N co-doped graphene nanotubes for all pH value electrochemical hydrogen evolution. Adv Energy Mater, 2017, 7: 1601671 CrossRef Google Scholar

[10] Yan H, Xie Y, Jiao Y, et al. Holey reduced graphene oxide coupled with an Mo2N-Mo2C heterojunction for efficient hydrogen evolution. Adv Mater, 2017, 30: 1704156 CrossRef PubMed Google Scholar

[11] Wu A, Xie Y, Ma H, et al. Integrating the active OER and HER components as the heterostructures for the efficient overall water splitting. Nano Energy, 2018, 44: 353-363 CrossRef Google Scholar

[12] Chen W, Pei J, He CT, et al. Rational design of single molybdenum atoms anchored on N-doped carbon for effective hydrogen evolution reaction. Angew Chem Int Ed, 2017, 56: 16086-16090 CrossRef PubMed Google Scholar

[13] Wang H, Min S, Wang Q, et al. Nitrogen-doped nanoporous carbon membranes with Co/CoP Janus-type nanocrystals as hydrogen evolution electrode in both acidic and alkaline environments. ACS Nano, 2017, 11: 4358-4364 CrossRef Google Scholar

[14] Zhang FS, Wang JW, Luo J, et al. Extraction of nickel from NiFe-LDH into Ni2P@NiFe hydroxide as a bifunctional electrocatalyst for efficient overall water splitting. Chem Sci, 2018, 9: 1375-1384 CrossRef PubMed Google Scholar

[15] Hinnemann B, Moses PG, Bonde J, et al. Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J Am Chem Soc, 2005, 127: 5308-5309 CrossRef PubMed Google Scholar

[16] Xie J, Zhang H, Li S, et al. Defect-rich MoS2 ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution. Adv Mater, 2013, 25: 5807-5813 CrossRef PubMed Google Scholar

[17] Guo Y, Tang J, Qian H, et al. One-pot synthesis of zeolitic imidazolate framework 67-derived hollow Co3S4@MoS2 heterostructures as efficient bifunctional catalysts. Chem Mater, 2017, 29: 5566-5573 CrossRef Google Scholar

[18] Meng C, Liu Z, Zhang T, et al. Layered MoS2 nanoparticles on TiO2 nanotubes by a photocatalytic strategy for use as high-performance electrocatalysts in hydrogen evolution reactions. Green Chem, 2015, 17: 2764-2768 CrossRef Google Scholar

[19] Zhao Z, Qin F, Kasiraju S, et al. Vertically aligned MoS2/Mo2C hybrid nanosheets grown on carbon paper for efficient electrocatalytic hydrogen evolution. ACS Catal, 2017, 7: 7312-7318 CrossRef Google Scholar

[20] Zheng X, Xu J, Yan K, et al. Space-confined growth of MoS2 nanosheets within graphite: the layered hybrid of MoS2 and graphene as an active catalyst for hydrogen evolution reaction. Chem Mater, 2014, 26: 2344-2353 CrossRef Google Scholar

[21] Hu WH, Han GQ, Dai FN, et al. Effect of pH on the growth of MoS2 (002) plane and electrocatalytic activity for HER. Int J Hydrogen Energy, 2016, 41: 294-299 CrossRef Google Scholar

[22] Shang X, Hu WH, Li X, et al. Oriented stacking along vertical (002) planes of MoS2: a novel assembling style to enhance activity for hydrogen evolution. Electrochim Acta, 2017, 224: 25-31 CrossRef Google Scholar

[23] Hu WH, Shang X, Xue J, et al. Activating MoS2/CNs by tuning (001) plane as efficient electrocatalysts for hydrogen evolution reaction. Int J Hydrogen Energy, 2017, 42: 2088-2095 CrossRef Google Scholar

[24] Liu Y, Zhou X, Ding T, et al. 3D architecture constructed via the confined growth of MoS2 nanosheets in nanoporous carbon derived from metal-organic frameworks for efficient hydrogen production. Nanoscale, 2015, 7: 18004-18009 CrossRef PubMed ADS Google Scholar

[25] Voiry D, Salehi M, Silva R, et al. Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Lett, 2013, 13: 6222-6227 CrossRef PubMed ADS Google Scholar

[26] Toh RJ, Sofer Z, Luxa J, et al. 3R phase of MoS2 and WS2 outperforms the corresponding 2H phase for hydrogen evolution. Chem Commun, 2017, 53: 3054-3057 CrossRef PubMed Google Scholar

[27] Ren X, Ma Q, Fan H, et al. A Se-doped MoS2 nanosheet for improved hydrogen evolution reaction. Chem Commun, 2015, 51: 15997-16000 CrossRef PubMed Google Scholar

[28] Wang H, Tsai C, Kong D, et al. Transition-metal doped edge sites in vertically aligned MoS2 catalysts for enhanced hydrogen evolution. Nano Res, 2015, 8: 566-575 CrossRef Google Scholar

[29] Li Y, Wang H, Xie L, et al. MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. J Am Chem Soc, 2011, 133: 7296-7299 CrossRef PubMed Google Scholar

[30] Zhou W, Zhou K, Hou D, et al. Three-dimensional hierarchical frameworks based on MoS2 nanosheets self-assembled on graphene oxide for efficient electrocatalytic hydrogen evolution. ACS Appl Mater Interfaces, 2014, 6: 21534-21540 CrossRef PubMed Google Scholar

[31] Zhu H, Du ML, Zhang M, et al. S-rich single-layered MoS2 nanoplates embedded in N-doped carbon nanofibers: efficient co-electrocatalysts for the hydrogen evolution reaction. Chem Commun, 2014, 50: 15435-15438 CrossRef PubMed Google Scholar

[32] Zhang G, Liu H, Qu J, et al. Two-dimensional layered MoS2: rational design, properties and electrochemical applications. Energy Environ Sci, 2016, 9: 1190-1209 CrossRef Google Scholar

[33] Zhou HC, Long JR, Yaghi OM. Introduction to metal–organic frameworks. Chem Rev, 2012, 112: 673-674 CrossRef PubMed Google Scholar

[34] Zhou HC, Kitagawa S. Metal–organic frameworks (MOFs). Chem Soc Rev, 2014, 43: 5415-5418 CrossRef PubMed Google Scholar

[35] Zhu QL, Xu Q. Metal-organic framework composites. Chem Soc Rev, 2014, 43: 5468-5512 CrossRef PubMed Google Scholar

[36] Cook TR, Zheng YR, Stang PJ. Metal-organic frameworks and self-assembled supramolecular coordination complexes: comparing and contrasting the design, synthesis, and functionality of metal-organic materials. Chem Rev, 2012, 113: 734-777 CrossRef PubMed Google Scholar

[37] Fang Z, Bueken B, De Vos DE, et al. Defect-engineered metal-organic frameworks. Angew Chem Int Ed, 2015, 54: 7234-7254 CrossRef PubMed Google Scholar

[38] Xia W, Mahmood A, Zou R, et al. Metal-organic frameworks and their derived nanostructures for electrochemical energy storage and conversion. Energy Environ Sci, 2015, 8: 1837-1866 CrossRef Google Scholar

[39] Mahmood A, Guo W, Tabassum H, et al. Metal-organic framework-based nanomaterials for electrocatalysis. Adv Energy Mater, 2016, 6: 1600423 CrossRef Google Scholar

[40] Liang Z, Qu C, Guo W, et al. Pristine metal-organic frameworks and their composites for energy storage and conversion. Adv Mater, 2018, 30: 1702891 CrossRef PubMed Google Scholar

[41] Zhang H, Osgood H, Xie X, et al. Engineering nanostructures of PGM-free oxygen-reduction catalysts using metal-organic frameworks. Nano Energy, 2017, 31: 331-350 CrossRef Google Scholar

[42] Cao X, Zheng B, Shi W, et al. Reduced graphene oxide-wrapped MoO3 composites prepared by using metal-organic frameworks as precursor for all-solid-state flexible supercapacitors. Adv Mater, 2015, 27: 4695-4701 CrossRef PubMed Google Scholar

[43] Zhao X, Zhu H, Yang X. Amorphous carbon supported MoS2 nanosheets as effective catalysts for electrocatalytic hydrogen evolution. Nanoscale, 2014, 6: 10680-10685 CrossRef PubMed ADS Google Scholar

[44] Srivastava SK, Kartick B, Choudhury S, et al. Thermally fabricated MoS2-graphene hybrids as high performance anode in lithium ion battery. Mater Chem Phys, 2016, 183: 383-391 CrossRef Google Scholar

[45] Wan Z, Shao J, Yun J, et al. Core-shell structure of hierarchical quasi-hollow MoS2 microspheres encapsulated porous carbon as stable anode for Li-ion batteries. Small, 2014, 10: 4975-4981 CrossRef PubMed Google Scholar

[46] Yi JD, Shi PC, Liang J, et al. Porous hollow MoS2 microspheres derived from core-shell sulfonated polystyrene microspheres@MoS2 nanosheets for efficient electrocatalytic hydrogen evolution. Inorg Chem Front, 2017, 4: 741-747 CrossRef Google Scholar

[47] Bian H, Ji Y, Yan J, et al. In situ synthesis of few-layered g-C3N4 with vertically aligned MoS2 loading for boosting solar-to-hydrogen generation. Small, 2018, 14: 1703003 CrossRef PubMed Google Scholar

[48] Wang H, Lu Z, Kong D, et al. Electrochemical tuning of MoS2 nanoparticles on three-dimensional substrate for efficient hydrogen evolution. ACS Nano, 2014, 8: 4940-4947 CrossRef PubMed Google Scholar

[49] Zhang Z, Li W, Yuen MF, et al. Hierarchical composite structure of few-layers MoS2 nanosheets supported by vertical graphene on carbon cloth for high-performance hydrogen evolution reaction. Nano Energy, 2015, 18: 196-204 CrossRef Google Scholar

[50] Khalid M, Honorato AMB, Varela H, et al. Multifunctional electrocatalysts derived from conducting polymer and metal organic framework complexes. Nano Energy, 2018, 45: 127-135 CrossRef Google Scholar

[51] Xia BY, Yan Y, Li N, et al. A metal–organic framework-derived bifunctional oxygen electrocatalyst. Nat Energy, 2016, 1: 15006 CrossRef ADS Google Scholar

[52] Chen R, Yang C, Cai W, et al. Use of platinum as the counter electrode to study the activity of nonprecious metal catalysts for the hydrogen evolution reaction. ACS Energy Lett, 2017, 2: 1070-1075 CrossRef Google Scholar

  • Figure 1

    (a) PXRD patterns of MoS2/C-X (X=400, 600, 800, 900, 1,000) and standard patterns of MoS2 (JCPDS card No. 73-1508). (b) Raman spectrum of MoS2/C-1000.

  • Scheme 1

    Schematic illustration of (a) the synthetic procedure of MoS2 nanorod and (b) the relative location of the reactants inside the furnace.

  • Figure 2

    (a) XPS survey spectrum of MoS2/C-1000. High-resolution C 1s (b), Mo 3d (c), and S 2p spectra (d) of MoS2/C-1000.

  • Figure 3

    (a, b) SEM images of Mo-MOF. (c, d) SEM images of MoS2/C-1000. (e) TEM and (f, g) HRTEM images of MoS2/C-1000. (h) The high angle annular dark-field scanning TEM image of MoS2/C-1000 and the corresponding elemental mapping of Mo, S and C, respectively. The scale bar in (h) is 100 nm.

  • Figure 4

    Electrocatalytic HER performance of MoS2/C-X (X = 400, 600, 800, 900, 1,000) and Pt/C in 0.5 mol L−1 H2SO4. (a) LSV curves of MoS2/C-1000 and MoS2/C-1000-mixed. (b) LSV curves of MoS2/C-X and Pt/C. (c) Overpotential at 10 mA cm−2 and the onset potential of MoS2/C-X. (d) The corresponding Tafel plots obtained from polarization curves. (e) Long-term cyclic voltammetry measurements of MoS2/C-1000. (f) Chronoamperometry data of MoS2/C-1000 and Pt/C conducted under η10.


Contact and support