Advertisement

Journal of Chemical Sciences

, 130:131 | Cite as

Remarkable photochemical HER activity of semiconducting 2H \(\hbox {MoSe}_{{2}}\) and \(\hbox {MoS}_{{2}}\) covalently linked to layers of 2D structures and of the stable metallic 1T phases prepared solvo- or hydro-thermally\(^{\S }\)

  • Navin Kumar Singh
  • Amit Soni
  • Reetendra Singh
  • Uttam Gupta
  • K Pramoda
  • C N R Rao
Regular Article
  • 194 Downloads

Abstract

\(\hbox {MoS}_{{2}}\) and \(\hbox {MoSe}_{{2}}\) in the stable semiconducting 2H form show negligible photocatalytic activity for the hydrogen evolution reaction (HER). By linking the layers of the dichalcogenide with layers of other 2D materials such as carbon-rich borocarbonitride (\(\hbox {BC}_{{7}}\hbox {N}\)), one can enhance the photochemical HER activity significantly. Interestingly, such nanocomposites, \(\hbox {MoSe}_{{2}}\)\(\hbox {MoSe}_{{2}}\) and \(\hbox {MoSe}_{{2}}\)–BCN show high photocatalytic activity even though the dichalcogenide itself is in the 2H form. This study shows the important role played by covalent cross-linking of layered compounds. Photocatalytic activity of covalently cross-linked layer of 2H-\(\hbox {MoSe}_{{2}}\) is higher than that of 2H-\(\hbox {MoS}_{{2}}\). Unlike the 2H forms, the metallic 1T forms of \(\hbox {MoS}_{{2}}\) and \(\hbox {MoSe}_{{2}}\) prepared by lithium intercalation followed by exfoliation, exhibit high photocatalytic HER activity. Unfortunately, materials prepared by lithium intercalation are unstable. The 1T forms of \(\hbox {MoSe}_{2}\) and \(\hbox {MoS}_{{2}}\) prepared by solvothermal or hydrothermal methods are, however, quite stable and exhibit good photochemical activity for HER. The 1T forms are generally superior to the covalently linked 2H forms. The present study shows how \(\hbox {MoSe}_{{2}}\) and \(\hbox {MoS}_{{2}}\) in both 2H and 1T forms can be exploited for photochemical HER activity by appropriate chemical manipulation.

Graphical Abstract

SYNOPSIS Photocatalytic HER activity of 2H-\(\hbox {MoSe}_{{2}}\) covalently linked with other 2D layered materials is superior to that of the pristine sheets. 1T-forms of \(\hbox {MoSe}_{2}\) and \(\hbox {MoS}_{{2}}\) grown by solvothermal or hydrothermal method show good photochemical activity. The present study shows that both \(\hbox {MoSe}_{{2}}\) and \(\hbox {MoS}_{{2}}\) in either 2H or 1T form can be exploited for photochemical HER activity by suitable chemical and physical manipulation.

Keywords

Photochemical hydrogen evolution Covalent cross-linking Borocarbonitrides Mo dichalcogenides 1T-\(\hbox {MoSe}_{{2}}\) 1T-\(\hbox {MoS}_{{2}}\) EDC coupling 

Notes

Acknowledgements

The authors would like to thank Mr. Swaraj Servottam for the Schemes.

Supplementary material

12039_2018_1533_MOESM1_ESM.pdf (719 kb)
Supplementary material 1 (pdf 718 KB)

References

  1. 1.
    Millet P, Ngameni R, Grigoriev S A, Mbemba N, Brisset F, Ranjbari A and Etievant C 2010 PEM water electrolyzers: From electrocatalysis to stack devolopement Int. J. Hydrog. Energy 35 5043CrossRefGoogle Scholar
  2. 2.
    Yu J G, Qi L F and Jaroniec M 2010 Hydrogen production by photocatalytic water splitting over Pt/\(\text{ TiO }_{{2}}\) nanosheets with exposed (001) facets J. Phys. Chem. C 114 13118CrossRefGoogle Scholar
  3. 3.
    Wang X, Maeda K, Thomas A, Takanabe K, Xin G, Carlsson J M, Domen K and Antonietti M 2009 A metal-free polymeric photocatalyst for hydrogen production from water under visible light Nat. Mater. 8 76CrossRefGoogle Scholar
  4. 4.
    Rao C N R, Lingampalli S R, Dey S and Roy A 2016 Solar photochemical and thermochemical splitting of water Philos. Trans. R. Soc. 374 20150088CrossRefGoogle Scholar
  5. 5.
    Gupta U, Naidu B S, Maitra U, Singh A, Shirodkar S N, Waghmare U V and Rao C N R 2014 Characterization of few-layer 1T-\(\text{ MoSe }_{{2}}\) and its superior performance in the visible-light induced hydrogen evolution reaction APL Mater. 2 092802CrossRefGoogle Scholar
  6. 6.
    Lei Z, Zhan J, Tang L, Zhang Y and Wang Y 2018 Recent development of metallic (1T) phase of molybdenum disulfide for energy conversion and storage Adv. Energy Mater. 8 1703482CrossRefGoogle Scholar
  7. 7.
    Pramoda K, Gupta U, Ahmad I, Kumar R and Rao C N R 2016 Assemblies of covalently cross-linked nanosheets of \(\text{ MoS }_{{2}}\) and of \(\text{ MoS }_{{2}}\)–RGO: synthesis and novel properties, J. Mater. Chem. A 4 8989CrossRefGoogle Scholar
  8. 8.
    Pramoda K, Gupta U, Chhetri M, Bandyopadhyay A, Pati S K and Rao C N R 2017 Nanocomposites of \(\text{ C }_{{3}}\text{ N }_{{4}}\) with layers of \(\text{ MoS }_{{2}}\) and nitrogenated RGO, obtained by covalent cross-linking: Synthesis, characterization, and HER activity ACS Appl. Mater. Interfaces 9 10664CrossRefGoogle Scholar
  9. 9.
    Pramoda K, Ayyub M M, Singh N K, Chhetri M, Gupta U, Soni A and Rao C N R 2017 Covalently bonded \(\text{ MoS }_{{2}}\)–borocarbonitride nanocomposites generated by using surface functionalities on the nanosheets and their remarkable HER activity J. Phys. Chem. C 122 1376Google Scholar
  10. 10.
    Singh N K, Pramoda K, Gopalakrishnan K and Rao C N R 2018 Synthesis, characterization, surface properties and energy device characterstics of 2D borocarbonitrides, (BN)\(_{{\rm x}}\text{ C }_{1-{\rm x}}\), covalently cross-linked with sheets of other 2D materials RSC Adv. 8 17237CrossRefGoogle Scholar
  11. 11.
    Nguyen T P, Choi S, Jeon J M, Kwon K C, Jang H W and Kim S Y 2016 Transition metal disulfide nanosheets synthesized by facile sonication method for the hydrogen evolution reaction J. Phys. Chem. C 120 3929CrossRefGoogle Scholar
  12. 12.
    Tsai C, Chan K, Abild-Pedersen F and Norskov J K 2014 Active edge sites in \(\text{ MoSe }_{{2}}\) and \(\text{ WSe }_{{2}}\) catalysts for the hydrogen evolution reaction: A density functional study Phys. Chem. Chem. Phys. 16 13156CrossRefGoogle Scholar
  13. 13.
    Srinivasu K, Modak B and Ghosh S K 2014 Porous graphitic carbon nitride: A possible metal-free photocatalyst for water splitting J. Phys. Chem. C 118 26479CrossRefGoogle Scholar
  14. 14.
    Zheng Y, Jiao Y, Zhu Y H, Li L H, Han Y, Chen Y, Du A J, Jaroniec M and Qiao S Z 2014 Hydrogen evolution by a metal-free electrocatalyst Nat. Commun. 5 3783CrossRefGoogle Scholar
  15. 15.
    Kumar N, Moses K, Pramoda K, Shirodkar S N, Mishra A K, Waghmare U V, Sundaresan A and Rao C N R 2013 Borocarbonitrides, \(\text{ B }_{{\rm x}}\text{ C }_{{\rm y}}\text{ N }_{{\rm z}}\) J. Mater. Chem. A 1 5806CrossRefGoogle Scholar
  16. 16.
    Barua M, Sreedhara M B, Pramoda K and Rao C N R 2017 Quantification of surface functionalities on graphene, boron nitride and borocarbonitrides by fluorescence labelling Chem. Phys. Lett. 683 459CrossRefGoogle Scholar
  17. 17.
    Yang W, Gan L, Li H and Zhai T 2016 Two-dimensional layered nanomaterials for gas-sensing applications Inorg. Chem. Front 3 433CrossRefGoogle Scholar
  18. 18.
    Radisavljevic B, Radenovic A, Brivio J, Giacometti V and Kis A 2011 Single-layer \(\text{ MoS }_{{2}}\) transistors Nat. Nanotechnol. 6 147CrossRefGoogle Scholar
  19. 19.
    Vishnoi P, Sampath A, Waghmare U V and Rao C N R 2017 Covalent functionalization of nanosheets of \(\text{ MoS }_{{2}}\) and \(\text{ MoSe }_{{2}}\) by substituted benzenes and other organic molecules Chem. Eur. J. 23 886CrossRefGoogle Scholar
  20. 20.
    Chhetri M, Maitra S, Chakraborty H, Waghmare U V and Rao C N R 2016 Superior performance of borocarbonitrides, \(\text{ B }_{{\rm x}}\text{ C }_{{\rm y}}\text{ N }_{{\rm z}}\), as stable, low-cost metal-free electrocatalysts for the hydrogen evolution reaction Energy Environ. Sci. 9 95CrossRefGoogle Scholar
  21. 21.
    Liu Q, Fang Q, Chu W, Wan Y, Li X, Xu W, Habib M, Tao S, Zhou Y, Liu D, Xiang T, Khalil A, Wu X, Chhowalla M, Ajayan P M and Song L 2017 Electron-doped 1T-\(\text{ MoS }_{{2}}\) via interface engineering for enhanced electrocatalytic hydrogen evolution Chem. Mater. 29 4739Google Scholar
  22. 22.
    Liu Z, Gao Z, Liu Y, Xia M, Wang R and Li N 2017 Heterogeneous nanostructure based on 1T-phase MoS\(_2\) for enhanced electrocatalytic hydrogen evolution ACS Appl. Mater. Interfaces 9 25291CrossRefGoogle Scholar
  23. 23.
    Mayo D W, Miller F A and Hannah R W 2004 Course Notes on the Interpretation of Infrared and Raman Spectra (Hoboken, NJ: John Wiley & Sons, Inc.) Ch. 1Google Scholar
  24. 24.
    Tonndorf P, Schmidt R, Böttger P, Xiao Zhang, Börner J, Liebig A, Albrecht M, Kloc C, Gordan O, Zahn D R T, Vasconcellos S M D and Bratschitsch R 2013 Photoluminescence emission and Raman response of \(\text{ MoS }_{{2}}\), \(\text{ MoSe }_{{2}}\), and \(\text{ WSe }_{{2}}\) nanolayers Opt. Express 21 4908CrossRefGoogle Scholar
  25. 25.
    Pramoda K, Kumar R and Rao C N R 2015 Graphene/single-walled carbon nanotube composites generated by covalent cross-linking Chem. Asian J10 2147CrossRefGoogle Scholar
  26. 26.
    Maitra U, Gupta U, De M, Datta R, Govindraj A and Rao C N R 2013 Highly effective visible-light-induced \(\text{ H }_{2}\) generation by single-layer 1T-\(\text{ MoS }_{2}\) and a nanocomposite of few-layer 2H-\(\text{ MoS }_{{2}}\) with heavily nitrogenated graphene Angew. Chem. Int. Ed. 52 13057CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2018

Authors and Affiliations

  • Navin Kumar Singh
    • 1
  • Amit Soni
    • 1
  • Reetendra Singh
    • 1
  • Uttam Gupta
    • 1
  • K Pramoda
    • 1
  • C N R Rao
    • 1
  1. 1.New Chemistry Unit, Chemistry and Physics of Materials Unit, Sheikh Saqr Laboratory and International Centre for Materials ScienceJawaharlal Nehru Centre for Advanced Scientific Research (JNCASR)BangaloreIndia

Personalised recommendations