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Co(Ni)–Mo–Sx Chalcogels Films as pH-Universal Electrocatalysts for the H2 Evolution Reaction

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Abstract

Here, a simple dipping coating route was applied to synthesize a series of CoMoSx/NiMoSx chalcogel thin film which in situ grown uniformly on the 3D skeleton of Ni foam as electrocatalysts for the hydrogen evolution reaction (HER). We attempt to understand the effect of pH on the kinetics of the HER. As expected, CoMoSx@Ni foam electrocatalyst presents a low overpotential of 118 mV at 10 mA cm−2 and a low Tafel slope of 85 mV dec−1 for HER in alkaline solution and an overpotential of 129 mV at 10 mA cm−2 and a low Tafel slope of 113 mV dec−1 for HER in acidic solution. The long-term performance of CoMoSx-3@Ni foam revealed that there was no obvious decrease in catalytic activity after 5000 cycles in alkaline medium. We are able to synthesize low-cost and pH-universal catalysts for efficient electrocatalytic production of hydrogen.

Graphic Abstract

A dipping coating route was applied to synthesize a series of chalcogel films in situ grown on 3D Ni foam skeleton as catalysts for HER. We attempt to understand the effect of pH on the kinetics of HER. CoMoSx as pH-universal catalyst presents a low overpotential and Tafel slope for HER.

HER polarization curves in 0.1 M KOH for chalcogel thin film on Ni foam, scan rate is 5 mV/s. And the inset images are TEM and simulative of chalcogel thin film

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References

  1. 1.

    Gandía LM, Oroz R, Ursúa A, Sanchis P, Diéguez PM (2007) Renewable hydrogen production: performance of an alkaline water electrolyzer working under emulated wind conditions. Energy Fuel 21:1699–1706

  2. 2.

    Subbaraman R, Tripkovic D, Strmcnik D, Chang KC, Uchimura M, Paulikas AP, Stamenkovic V, Markovic NM (2011) Enhancing hydrogen evolution activity in water splitting by tailoring Li+-Ni(OH)2-Pt interfaces. Science 334:1256–1260

  3. 3.

    Subbaraman R, Dusan T, Kee-Chul C, Dusan S, Pussana H, Maria C, Jeff GV, Stamenkovic V, Nenad M (2012) Trends in activity for the water electrolyser reactions on 3d M (Ni Co, Fe, Mn) hydr(oxy)oxide catalysts. Nat Mater 11:550–557

  4. 4.

    Han Q, Liu K, Chen J, Wei X (2003) Hydrogen evolution reaction on amorphous Ni-S-Co alloy in alkaline medium. Int J Hydrog Energy 28:1345–1352

  5. 5.

    Birry L, Lasia A (2004) Studies of the hydrogen evolution reaction on Raney nickel-molybdenum electrodes. J Appl Electrochem 34:735–749

  6. 6.

    Lasia A, Rami A (1990) Kinetics of hydrogen evolution on nickel electrodes. J Electroanal Chem Interfacial Electrochem 294:123–141

  7. 7.

    Greeley J, Jaramillo TF, Bonde J, Norskov J (2006) Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat Mater 5:909–913

  8. 8.

    Jaramillo TF, Bonde J, Nielsen JH, Horch S, Chorkendorff I (2007) Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317:100–102

  9. 9.

    Kibsgaard J, Jaramillo TF, Besenbacher F (2014) Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo3S13]2− clusters. Nat Chem 6:248–253

  10. 10.

    Kibsgaard J, Chen Z, Reinecke BN, Jaramillo TF (2012) Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat Mater 11:963–969

  11. 11.

    Faber MS, Lukowski MA, Ding Q, Kaiser NS, Jin S (2014) Earth-abundant metal pyrites (FeS2, CoS2, NiS2, and their alloys) for highly efficient hydrogen evolution and polysulfide reduction electrocatalysis. J Phys Chem C 118:21347–21356

  12. 12.

    Carlos G, Morales G, Hu XL (2018) Amorphous molybdenum sulfides as hydrogen evolution catalysts. Acc Chem Res 47:2671–2681

  13. 13.

    Park SW, Park JS, Abroshan H, Zhang L, KiM JK, Zhang JM, Guo JH, Siahrostami S, Zheng XL (2018) Enhancing catalytic activity of MoS2 basal plane S-vacancy by Co cluster addition. ACS Energy Lett 3:2685–2693

  14. 14.

    Wiensch J, John J, Torelli DA, Vesus MV (2017) Comparative study in acidic and alkaline media of the effects of pH and crystallinity on the hydrogen-evolution reaction on MoS2 and MoSe2. ACS Energy Lett 2:2234–2238

  15. 15.

    Ding Q, Song B, Xu P, Jin S (2016) Efficient electrocatalytic and photoelectrochemical hydrogen generation using MoS2 and related compounds. Chemistry 1:699–726

  16. 16.

    Faber MS, Dziedzic R, Lukowski MA, Kaiser NS, Ding Q, Jin Q (2014) High-performance electrocatalysis using metallic cobalt pyrite (CoS2) micro- and nanostructures. J Am Chem Soc 136:10053–10061

  17. 17.

    Lauritsen J, Bollinger MV, Lagsgaard E, Jacobsen KW, Clausen BS, Besenbacher F (2001) Atomic-scale structure of Co–Mo–S nanoclusters in hydrotreating catalysts. J Catal 197:1–5

  18. 18.

    Lauritsen J, Bollinger MV, Lagsgaard E, Jacobsen KW, Clausen BS, Besenbacher F (2007) Location and coordination of promoter atoms in Co- and Ni-promoted MoS2-based hydrotreating catalysts. J Catal 249:220–233

  19. 19.

    Topsøe H (2007) The role of Co–Mo–S type structures in hydrotreating catalysts. Appl Catal A 322:3–8

  20. 20.

    Hinnemann B, Moses PG, Bonde J, Jrgensen KP, Nielsen JH, Horch S, Chorkendorff I, Nirskov JK (2005) Biomimetic hydrogen evolution MoS2 nanoparticles as catalyst for hydrogen evolution. J Am Chem Soc 127:5308–5309

  21. 21.

    Raybaud P, Hafner J, Kresse G, Kasztelan S, Toulhoat H (2000) Ab initio study of the H2-H2S/MoS2 gas-solid interface: the nature of the catalytically active sites. J Catal 189:129–146

  22. 22.

    Huang Y, Nielsen RJ, Goddard WA, Soriaga MP (2015) The reaction mechanism with free energy barriers for electrochemical dihydrogen evolution on MoS2. J Am Chem Soc 137:6692–6698

  23. 23.

    Jakub SJ, Mercouri GK, Nenad MM (2015) Design of active and stable Co–Mo–Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction. Nat Mater 15:1–6

  24. 24.

    Hou JG, Sun YQ, Cao SY, Wu YZ, Chen H, Sun LC (2017) Regulated synthesis of Mo sheets and their derivative MoX sheets (X: P, S, or C) as efficient electrocatalysts for hydrogen evolution reactions. ACS Appl Mater Interfaces 9:8041–8046

  25. 25.

    Lay MD, Varazo K, Stickney JL (2003) Formation of sulfur atomic layers on gold from aqueous solutions of sulfide and thiosulfate? Studies using EC-STM, UHV-EC, and TLEC. Langmuir 19:8416–8427

  26. 26.

    Weber T, Muijsers JC, Niemantsverdriet JW (1995) Structure of amorphous MoS3. J Phys Chem 99:9194–9200

  27. 27.

    Jirkovsky JS, Björling A, Ahlberg E (2012) Reduction of oxygen on dispersed nanocrystalline CoS2. J Phys Chem C 116:24436–24444

  28. 28.

    Li J, Wang YC, Zhou T, Zhang H, Sun X, Tang J, Zhang L, Al-Enizi AM, Yang Z, Zheng GF (2015) Nanoparticle superlattices as efficient bifunctional electrocatalyst for water splitting. J Am Chem Soc 137:14305–14312

  29. 29.

    Wang JR, Osterloh FE (2014) Limiting factors for photochemical charge separation in BiVO4/Co3O4, a highly active photocatalyst for water oxidation in sunlight. J Mater Chem A 2:9405–9411

  30. 30.

    Paracchino A, Laporte V, Sivula K, Grzel M, Thimsen E (2011) Highly active oxide photocathode for photoelectrochemical water reduction. Nat Mater 8:456–461

  31. 31.

    Xu Y, Schoonen MAA (2000) Absolute energy position of conduction and valence bands of selected semiconducting minerals. Am Miner 85:543–556

  32. 32.

    Liao L, Zhang Q, Su Z, Zhao Z, Wang Y, Li Y, Lu X, Wei D, Feng G, Yu Q, Cai X, Zhao J, Ren Z, Fang H, Robles-Hernandez F, Baldelli S, Bao J (2014) Efficient solar water-splitting using a nanocrystalline CoO photocatalyst. Nat Nanotechnol 9:69–73

  33. 33.

    Ledendecker M, Krick Calderyn S, Papp C, Steinrk H, Antonietti M, Shalom M (2015) The synthesis of nanostructured Ni5P4 films and their use as a non-noble bifunctional electrocatalyst for full water splitting. Angew Chem Int Ed 54:12361–12365

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Acknowledgements

This work was supported by the Doctoral Research Foundation of Zaozhuang University (2018BS056), China Postdoctoral Science Foundation Funded Project (2018M632635) and National Natural Science Foundation of China for Youths (61904177).

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Correspondence to Yanbiao Ren or Xiaowu He.

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Ren, Y., Zhang, L. & He, X. Co(Ni)–Mo–Sx Chalcogels Films as pH-Universal Electrocatalysts for the H2 Evolution Reaction. Catal Lett 150, 623–630 (2020). https://doi.org/10.1007/s10562-019-02961-x

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Keywords

  • Chalcogel thin film
  • Electro-catalyst
  • Hydrogen evolution reaction
  • Overpotential
  • Tafel slope