Skip to main content

Intercalation makes the difference with TiS2: Boosting electrocatalytic water oxidation activity through Co intercalation

  • Aron J. Huckaba (a1), Maryline Ralaiarisoa (a2), Kyung Taek Cho (a1), Emad Oveisi (a3), Norbert Koch (a2) and Mohammad Khaja Nazeeruddin (a1)...

Intercalated and unmodified TiS2 nanomaterials were synthesized and characterized by UV-Visible-NIR spectroscopy, Powder X-Ray Diffraction, and X-Ray Photoelectron and Ultraviolet Photoelectron Spectroscopy. Photoelectron spectroscopy measurements indicated that CoS and Cu2S appeared to be intercalated between sheets of partially or fully oxidized TiS2, which could be solution processed on conductive oxide substrates. The materials were then applied toward water oxidation and evaluated by cyclic voltammetry, chronoamperometry, and impedance measurements. While unmodified TiS2 was not observed to perform well as an electrocatalyst with overpotentials >3 V in 1 M NaOH electrolyte, CoS intercalation was found to lower the overpotential by ∼1.8–1.44 V at 10 mA/cm2. Conversely, Cu2S intercalation resulted in only a modest increase in performance (>2.3 V overpotential). Impedance measurements indicated that intercalation increased the series resistance in the as-prepared samples but decreased the series resistance in oxidized samples.

  • View HTML
    • Send article to Kindle

      To send this article to your Kindle, first ensure is added to your Approved Personal Document E-mail List under your Personal Document Settings on the Manage Your Content and Devices page of your Amazon account. Then enter the ‘name’ part of your Kindle email address below. Find out more about sending to your Kindle. Find out more about sending to your Kindle.

      Note you can select to send to either the or variations. ‘’ emails are free but can only be sent to your device when it is connected to wi-fi. ‘’ emails can be delivered even when you are not connected to wi-fi, but note that service fees apply.

      Find out more about the Kindle Personal Document Service.

      Intercalation makes the difference with TiS2: Boosting electrocatalytic water oxidation activity through Co intercalation
      Available formats
      Send article to Dropbox

      To send this article to your Dropbox account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your <service> account. Find out more about sending content to Dropbox.

      Intercalation makes the difference with TiS2: Boosting electrocatalytic water oxidation activity through Co intercalation
      Available formats
      Send article to Google Drive

      To send this article to your Google Drive account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your <service> account. Find out more about sending content to Google Drive.

      Intercalation makes the difference with TiS2: Boosting electrocatalytic water oxidation activity through Co intercalation
      Available formats
Corresponding author
a) Address all correspondence to this author. e-mail:
Hide All

Contributing Editor: Artur Braun

Hide All
1. Walter, M.G., Warren, E.L., McKone, J.R., Boettcher, S.W., Mi, Q., Santori, E.A., and Lewis, N.S.: Solar water splitting cells. Chem. Rev. 110, 6446 (2010).
2. Eisenberg, R. and Gray, H.B.: Preface on making oxygen. Inorg. Chem. 47, 1697 (2008).
3. Hunter, B.M., Gray, H.B., and Mu, A.M.: Earth-Abundant Heterogeneous Water Oxidation Catalysts. Chem. Rev. 116, 14120 (2016).
4. Artero, V. and Fontecave, M.: Solar fuels generation and molecular systems: Is it homogeneous or heterogeneous catalysis? Chem. Soc. Rev. 42, 2338 (2013).
5. Rosser, T. and Reisner, E.: Understanding immobilized molecular catalysts for fuel-forming reactions through UV/vis spectroelectrochemistry. ACS Catal. 7, 3131 (2017).
6. Umena, Y., Kawakami, K., Shen, J-R., and Kamiya, N.: Crystal structure of oxygen-evolving photosystem II at a resolution of 1.9 Å. Nature 473, 55 (2011).
7. Kok, B., Forbush, B., and McGloin, M.: Cooperation of charges in photosynthetic O2 evolution–I. A linear four step mechanism. Photochem. Photobiol. 11, 457 (1970).
8. Fujishima, A. and Honda, K.: Electrochemical photolysis of water at a semiconductor electrode. Nature 238, 37 (1972).
9. Blakemore, J.D., Crabtree, R.H., and Brudvig, G.W.: Molecular catalysts for water oxidation. Chem. Rev. 115, 12974 (2015).
10. Yagi, M. and Kaneko, M.: Molecular catalysts for water oxidation. Chem. Rev. 101, 21 (2001).
11. Hoare, J.P.: The Electrochemistry of Oxygen (John Wiley and Sons, Inc., New York, 1968).
12. Lian, K., Thorpe, S.J., and Kirk, D.W.: The electrocatalytic activity of amorphous and crystalline Ni–Co alloys on the oxygen evolution reaction. Electrochim. Acta 37, 169 (1992).
13. Suntivich, J., May, K.J., Gasteiger, H.A., Goodenough, J.B., and Shao-Horn, Y.: A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 334, 1383 (2011).
14. Bockris, J.O. and Otagawa, T.: Mechanism of oxygen evolution on perovskites. J. Phys. Chem. 87, 2960 (1983).
15. Driess, M., Menezes, P.W., Indra, A., Gutkin, V., and Driess, M.: Boosting electrochemical water oxidation through replacement of Oh Co sites in cobalt oxide spinel with manganese. Chem. Commun. 53, 8018 (2017).
16. McCrory, C.C.L., Jung, S., Peters, J.C., and Jaramillo, T.F.: Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J. Am. Chem. Soc. 135, 16977 (2013).
17. Trasatti, S.: Electrocatalysis by oxides—Attempt at a unifying approach. J. Electroanal. Chem. Interfacial Electrochem. 111, 125 (1980).
18. Zahran, Z.N., Mohamed, E.A., Ohta, T., and Naruta, Y.: Electrocatalytic water oxidation by a highly active and robust α-Mn2O3 thin film sintered on a fluorine-doped tin oxide electrode. ChemCatChem 8, 532 (2016).
19. Blakemore, J.D., Gray, H.B., Winkler, J.R., and Mu, A.M.: Co3O4 nanoparticle water-oxidation catalysts made by pulsed-laser ablation in liquids. ACS Catal. 3, 2497, (2013).
20. Liang, H., Meng, F., Cabán-Acevedo, M., Li, L., Forticaux, A., Xiu, L., Wang, Z., and Jin, S.: Hydrothermal continuous flow synthesis and exfoliation of NiCo layered double hydroxide nanosheets for enhanced oxygen evolution catalysis. Nano Lett. 15, 1421 (2015).
21. Li, D., Baydoun, H., Verani, N., and Brock, S.L.: Efficient water oxidation using CoMnP nanoparticles. J. Am. Chem. Soc. 138, 4006 (2016).
22. Mendoza-Garcia, A., Zhu, H., Yu, Y., Li, Q., Zhou, L., Su, D., Kramer, M.J., and Sun, S.: Controlled anisotropic growth of Co–Fe–P from Co–Fe–O nanoparticles. Angew. Chem., Int. Ed. 54, 9642 (2015).
23. Jeong, D., Jin, K., Jerng, S.E., Seo, H., Kim, D., Nahm, S.H., Kim, S.H., and Nam, K.T.: Mn5O8 nanoparticles as efficient water oxidation catalysts at neutral pH. ACS Catal. 5, 4624 (2015).
24. 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., and Bao, J.: Efficient solar water-splitting using a nanocrystalline CoO photocatalyst. Nat. Nanotechnol. 9, 69 (2014).
25. Whittingham, M.S.: Electrical energy storage and intercalation chemistry. Science 192, 1126 (1976).
26. Whittingham, M.S.: Lithium batteries and cathode materials. Chem. Rev. 104, 4271 (2004).
27. Conroy, L.E. and Park, K.C.: Electrical properties of the group IV disulfides, titanium disulfide, zirconium disulfide, hafnium disulfide and tin disulfide. Inorg. Chem. 7, 459 (1968).
28. Choi, W., Choudhary, N., Han, G.H., Park, J., Akinwande, D., and Lee, Y.H.: Recent development of two-dimensional transition metal dichalcogenides and their applications. Mater. Today 20, 116 (2017).
29. Bonaccorso, F., Sun, Z., Hasan, T., and Ferrari, A.C.: Graphene photonics and optoelectronics. Nat. Photonics 4, 611 (2010).
30. Jung, Y., Zhou, Y., and Cha, J.J.: Intercalation in two-dimensional transition metal chalcogenides. Inorg. Chem. Front. 3, 452 (2016).
31. Lindic, M.H., Pecquenard, B., Vinatier, P., Levasseur, A., Martinez, H., Gonbeau, D., Petit, P.E., and Ouvrard, G.: Electrochemical mechanisms during lithium insertion into TiO0.6S2.8 thin film positive electrode in lithium microbatteries. J. Electrochem. Soc. 152, A141 (2005).
32. Scholz, G., Joensen, P., Reyes, J.M., and Frindt, R.F.: Intercalation of Ag in TaS2 and TiS2 . Physica B+C 105, 214 (1981).
33. Wiegers, G.A.: Misfit layer compounds: Structures and physical properties. Prog. Solid State Chem. 24, 1 (1996).
34. Tian, B., Tang, W., Leng, K., Chen, Z., Tan, S.J.R., Peng, C., Ning, G-H., Fu, W., Su, C., Zheng, G.W., and Loh, K.P.: Phase transformations in TiS2 during K intercalation. ACS Energy Lett. 2, 1835 (2017).
35. Guilmeau, E., Maignan, A., Wan, C., and Koumoto, K.: On the effects of substitution, intercalation, non-stoichiometry and block layer concept in TiS2 based thermoelectrics. Phys. Chem. Chem. Phys. 17, 24541 (2015).
36. Prabakar, S., Bumby, C.W., and Tilley, R.D.: Liquid-phase synthesis of flower-like and flake-like titanium disulfide nanostructures. Chem. Mater. 21, 1725 (2009).
37. Toh, R.J., Sofer, Z., and Pumera, M.: Catalytic properties of group 4 transition metal dichalcogenides (MX2; M = Ti, Zr, Hf; X = S, Se, Te). J. Mater. Chem. A 4, 18322 (2016).
38. Huckaba, A.J., Gharibzadeh, S., Ralaiarisoa, M., Roldan-Carmona, C., Mohammadian, N., Grancini, G., Lee, Y., Amsalem, P., Plichta, E.J., Koch, N., Moshaii, A., and Nazeeruddin, M.K.: Low cost TiS2 as hole transport material for perovskite solar cells. Small Methods, doi: 10.1002/smtd.201700250. (2017).
39. Park, K.H., Choi, J., Kim, H.J., Oh, D-H., Ahn, J.R., and Son, S.U.: Unstable single-layered colloidal TiS2 nanodisks. Small 4, 945 (2008).
40. Kirmani, A.R., Carey, G.H., Abdelsamie, M., Yan, B., Cha, D., Rollny, L.R., Cui, X., Sargent, E.H., and Amassian, A.: Effect of solvent environment on colloidal-quantum-dot solar-cell manufacturability and performance. Adv. Mater. 26, 4717 (2014).
41. Let, A.L., Mainwaring, D.E., Rix, C.J., and Murugaraj, P.: Thio sol–gel synthesis of titanium disulfide thin films and nanoparticles using titanium(IV) alkoxide precursors. J. Phys. Chem. Solids 68, 1428 (2007).
42. Cui, Q., Sakhdari, M., Chamlagain, B., Chuang, H-J., Liu, Y., Cheng, M.M-C., Zhou, Z., and Chen, P-Y.: Ultrathin and atomically flat transition-metal oxide: Promising building blocks for metal–insulator electronics. ACS Appl. Mater. Interfaces 8, 34552 (2016).
43. Jeong, S., Yoo, D., Ahn, M., Miró, P., Heine, T., and Cheon, J.: Tandem intercalation strategy for single-layer nanosheets as an effective alternative to conventional exfoliation processes. Nat. Commun. 6, 5763 (2015).
44. Chen, L., Rahme, K., Holmes, J.D., Morris, M.A., and Slater, N.K.H.: Non-solvolytic synthesis of aqueous soluble TiO2 nanoparticles and real-time dynamic measurements of the nanoparticle formation. Nanoscale Res. Lett. 7, 297 (2012).
45. Morasse, R.A.L., Li, T., Baum, Z.J., and Goldberger, J.E.: Rational synthesis of dimensionally reduced TiS2 phases. Chem. Mater. 26, 4776 (2014).
46. Muller, G.A., Cook, J.B., Kim, H-S., Tolbert, S.H., and Dunn, B.: High performance pseudocapacitor based on 2D layered metal chalcogenide nanocrystals. Nano Lett. 15, 1911 (2015).
47. Mousavi-Kamazani, M., Zarghami, Z., and Salavati-Niasari, M.: Facile and novel chemical synthesis, characterization, and formation mechanism of copper sulfide (Cu2S, Cu2S/CuS, CuS) nanostructures for increasing the efficiency of solar cells. J. Phys. Chem. C 120, 2096 (2016).
48. Ramasamy, K., Malik, M.A., Raftery, J., Tuna, F., and O’Brien, P.: Selective deposition of cobalt sulfide nanostructured thin films from single-source precursors. Chem. Mater. 22, 4919 (2010).
49. Let, A.L., Mainwaing, D., Rix, C., and Murugaraj, P.: Synthesis and optical properties of TiS2 nanoclusters. Rev. Roum. Chim. 52, 235 (2007).
50. Moulder, J.F., Stickle, W.F., Sobol, P.E., and Bomben, K.D.: Handbook of X-Ray Photoelectron Spectroscopy (Heyden and Son, Eden Prairie, Minnesota, 1995).
51. Carley, A.F., Chalker, P.R., Riviere, J.C., and Roberts, M.W.: The identification and characterisation of mixed oxidation states at oxidised titanium surfaces by analysis of X-ray photoelectron spectra. J. Chem. Soc., Faraday Trans. 1 83, 351 (1987).
52. Xu, W., Zhu, S., Liang, Y., Li, Z., Cui, Z., Yang, X., and Inoue, A.: Nanoporous CuS with excellent photocatalytic property. Sci. Rep. 5, srep18125 (2015).
53. Gopalakrishnan, J., Murugesan, T., Hegde, M.S., and Rao, C.N.R.: Study of transition-metal monosulphides by photoelectron spectroscopy. J. Phys. C: Solid State Phys. 12, 5255 (1979).
54. Battistoni, C., Gastaldi, L., Mattogno, G., Simeone, M.G., and Viticoli, S.: Structural and magnetic properties of layer compounds: CoGaInS4 . Solid State Commun. 61, 43 (1987).
55. Gonbeau, D., Guimon, C., Pfister-Guillouzo, G., Levasseur, A., Meunier, G., and Dormoy, R.: XPS study of thin films of titanium oxysulfides. Surf. Sci. Lett. 254, A476 (1991).
56. Zhao, X., Jiang, J., Xue, Z., Yan, C., and Mu, T.: An ambient temperature, CO2-assisted solution processing of amorphous cobalt sulfide in a thiol/amine based quasi-ionic liquid for oxygen evolution catalysis. Chem. Commun. 68, 9418 (2017).
57. Smith, R.D.L., Prévot, M.S., Fagan, R.D., Trudel, S., Berlinguette, C.P., Pre, M.S., Fagan, R.D., and Trudel, S.: Water oxidation catalysis: Electrocatalytic response to metal stoichiometry in amorphous metal oxide films containing iron, cobalt, and nickel. J. Am. Chem. Soc. 135, 11580 (2013).
Recommend this journal

Email your librarian or administrator to recommend adding this journal to your organisation's collection.

Journal of Materials Research
  • ISSN: 0884-2914
  • EISSN: 2044-5326
  • URL: /core/journals/journal-of-materials-research
Please enter your name
Please enter a valid email address
Who would you like to send this to? *


Type Description Title
Supplementary materials

Huckaba et al supplementary material
Huckaba et al supplementary material 1

 Word (7.1 MB)
7.1 MB


Full text views

Total number of HTML views: 71
Total number of PDF views: 155 *
Loading metrics...

Abstract views

Total abstract views: 550 *
Loading metrics...

* Views captured on Cambridge Core between 16th November 2017 - 20th September 2018. This data will be updated every 24 hours.