Catalysis Letters

, Volume 148, Issue 10, pp 3126–3133 | Cite as

Water Adsorption and Decomposition on Co(0001) Surface: A Computational Study

  • Minhua Zhang
  • Heyuan Huang
  • Yingzhe Yu


Water adsorption and decomposition on the Co(0001) surface has been systematically studied by spin-polarized density functional theory calculations and atomic thermodynamics. H2O adsorption mechanism has been analyzed by partial density of states. The possible structure of adsorbed H2O molecules comprised of monomer-hexamer have been investigated and the phase diagram shows that only two configurations are stable thermodynamically: clean Co(0001) surface and H2O hexamer adsorption. The competition between the ability of a H2O molecule to bond with the substrate and its ability to act as a H-bond acceptor leads to the symmetry-breaking bond alteration in the hexamer structure. In addition, the interaction among adsorbed H2O molecules can help stabilize adsorption configurations by forming H-bonds. Presence of O species has a great influence on the decomposition of water and can significantly lower the activation barrier of H–OH bond cleavage.

Graphical Abstract


Water adsorption Water decomposition Co(0001) surface First-principle 


Compliance with Ethical Standards

Conflict of interest

There is no conflict of interest about this article.

Supplementary material

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Supplementary material 1 (DOCX 7228 KB)


  1. 1.
    Thiel PA, Madey TE (1987) The interaction of water with solid surfaces: fundamental aspects. Surf Sci Rep 7:211–385CrossRefGoogle Scholar
  2. 2.
    Verdaguer A, Sacha GM, Bluhm H, Salmeron M (2006) Molecular structure of water at interfaces: wetting at the nanometer scale. Chem Rev 106:1478–1510CrossRefPubMedGoogle Scholar
  3. 3.
    Michaelides A (2006) Density functional theory simulations of water-metal interfaces: waltzing waters, a novel 2D ice phase, and more. Appl Phys A 85:415–425CrossRefGoogle Scholar
  4. 4.
    Morgenstern K, Nieminen J (2004) Imaging water on Ag(111): field induced reorientation and contrast inversion. J Chem Phys 120:10786–10791CrossRefPubMedGoogle Scholar
  5. 5.
    Nie S, Feibelman PJ, Bartelt NC, Thürmer K (2010) Pentagons and heptagons in the first water layer on Pt(111). Phys Rev Lett 105:1–4CrossRefGoogle Scholar
  6. 6.
    Mitsui T, Rose MK, Fomin E et al (2002) Water diffusion and clustering on Pd(111). Science 297:1850–1852CrossRefPubMedGoogle Scholar
  7. 7.
    Michaelides A, Morgenstern K (2007) Ice nanoclusters at hydrophobic metal surfaces. Nat Mater 6:597–601CrossRefPubMedGoogle Scholar
  8. 8.
    Carrasco J, Michaelides A, Forster M et al (2009) A one-dimensional ice structure built from pentagons. Nat Mater 8:427–431CrossRefPubMedGoogle Scholar
  9. 9.
    Shiotari A, Sugimoto Y (2017) Ultrahigh-resolution imaging of water networks by atomic force microscopy. Nat Commun 8:1–7CrossRefGoogle Scholar
  10. 10.
    Komeda T, Fukidome H, Kim Y et al (2002) Scanning tunneling microscopy study of water molecules on Pd(110) at cryogenic temperature. Jpn J Appl Phys 41:4932–4935CrossRefGoogle Scholar
  11. 11.
    Nezafati M, Cho K, Giri A, Kim C (2016) DFT study on the water molecule adsorption and the surface dissolution behavior of Mg alloys. Mater Chem Phys 182:347–358CrossRefGoogle Scholar
  12. 12.
    Ren J, Meng S (2006) Atomic structure and bonding of water overlayer on Cu(110): the borderline for intact and dissociative adsorption. J Am Chem Soc 128:9282–9283CrossRefPubMedGoogle Scholar
  13. 13.
    Tang QL, Chen ZX (2007) Influence of aggregation, defects, and contaminant oxygen on water dissociation at Cu(110) surface: a theoretical study. J Chem Phys 127:104707CrossRefPubMedGoogle Scholar
  14. 14.
    Yu X, Zhang X, Wang H, Feng G (2017) High coverage water adsorption on the CuO(111) surface. Appl Surf Sci 425:803–810CrossRefGoogle Scholar
  15. 15.
    Hodgson A, Haq S (2009) Water adsorption and the wetting of metal surfaces. Surf Sci Rep 64:381–451CrossRefGoogle Scholar
  16. 16.
    Tu YB, Tao ML, Sun K, Wang JZ (2018) Effects of an electric field on the adsorption of water molecules on the Cd(0001) surface. Surf Sci 668:1–6CrossRefGoogle Scholar
  17. 17.
    Meng S, Wang EG, Gao S (2004) Water adsorption on metal surfaces: a general picture from density functional theory studies. Phys Rev B 69:1–13CrossRefGoogle Scholar
  18. 18.
    Wang H, Sun X, Han E-H (2018) The interactions between high temperature water and Fe3O4(111) by first-principles molecular dynamics simulation. Int J Electrochem Sci 13:2430–2440CrossRefGoogle Scholar
  19. 19.
    Mirabella F, Zaki E, Ivars-Barceló F et al (2018) Cooperative formation of long-range ordering in water ad-layers on Fe3O4(111) surfaces. Angew Chem Int Ed 57:1409–1413CrossRefGoogle Scholar
  20. 20.
    Iglesia E (1997) Design, synthesis, and use of cobalt-based Fischer-Tropsch synthesis catalysts. Appl Catal A 161:59–78CrossRefGoogle Scholar
  21. 21.
    Torres Galvis HM, De Jong KP (2013) Catalysts for production of lower olefins from synthesis gas: a review. ACS Catal 3:2130–2149CrossRefGoogle Scholar
  22. 22.
    Ruckenstein E, Wang HY (2002) Carbon deposition and catalytic deactivation during CO2 reforming of CH4 over Co/γ-Al2O3 catalysts. J Catal 205:289–293CrossRefGoogle Scholar
  23. 23.
    Heras JM, Papp H, Spiess W (1982) Face specificity of the H2O adsorption and decomposition on Co surfaces—a LEED, UPS, sp and TPD study. Surf Sci 117:590–604CrossRefGoogle Scholar
  24. 24.
    Grellner F, Klingenberg B, Borgmann D, Wedler G (1994) Interaction of H2O with Co(1120): a photoelectron spectroscopic study. Surf Sci 312:143–150CrossRefGoogle Scholar
  25. 25.
    Xu L, Ma Y, Zhang Y et al (2010) Water Adsorption on a Co (0001) Surface. J Phys Chem C 114:17023–17029CrossRefGoogle Scholar
  26. 26.
    Heras JM, Albano EV (1981) Work function changes of cobalt films at 77 K upon water adsorption. Appl Surf Sci 7:332–346CrossRefGoogle Scholar
  27. 27.
    Sun C, Liu L-M, Selloni A et al (2010) Titania-water interactions: a review of theoretical studies. J Mater Chem 20:10319CrossRefGoogle Scholar
  28. 28.
    Calzolari A, Catellani A (2009) Water adsorption on nonpolar ZnO(1010) surface: a microscopic understanding. J Phys Chem C 113:2896–2902CrossRefGoogle Scholar
  29. 29.
    Parkinson GS (2016) Iron oxide surfaces. Surf Sci Rep 71:272–365CrossRefGoogle Scholar
  30. 30.
    Liu H, Di Valentin C (2018) Bulk-terminated or reconstructed Fe3O4(001) surface: water makes a difference. Nanoscale 4:11021–11027CrossRefGoogle Scholar
  31. 31.
    Meier M, Hulva J, Jakub Z et al (2018) Water agglomerates on Fe3O4 (001). Proc Natl Acad Sci USA 115:E5642–E5650CrossRefPubMedGoogle Scholar
  32. 32.
    Parkinson GS, Dohnalek Z, Smith RS, Kay BD (2010) Reactivity of Fe0 atoms with and clusters with D2O over FeO(111). J Phys Chem C 114:17136–17141CrossRefGoogle Scholar
  33. 33.
    Schwarz M, Faisal F, Mohr S et al (2018) Structure-dependent dissociation of water on cobalt oxide. J Phys Chem Lett 2018:4–10Google Scholar
  34. 34.
    Delley B (1990) An all-electron numerical method for solving the local density functional for polyatomic molecules. J Chem Phys 508:508–517CrossRefGoogle Scholar
  35. 35.
    Delley B (2000) From molecules to solids with the from molecules to solids with the DMol3 approach. J Chem Phys 113:7756–7764CrossRefGoogle Scholar
  36. 36.
    Pack JD, Monkhorst HJ (1977) Special points for Brillouin-zone integrations. Phys Rev B 16:1748–1749CrossRefGoogle Scholar
  37. 37.
    Halgren TA, Lipscohlb WN (1977) The synchronous-transit method for determining reaction pathways and locating molecular transition states. Chem Phys Lett 49:225–232CrossRefGoogle Scholar
  38. 38.
    Michaelides A (2007) Simulating ice nucleation, one molecule at a time, with the “DFT microscope”. Faraday Discuss 136:287–297CrossRefPubMedGoogle Scholar
  39. 39.
    Merte LR, Bechstein R, Peng G et al (2014) Water clustering on nanostructured iron oxide films. Nat Commun 5:1–9CrossRefGoogle Scholar
  40. 40.
    Reuter K, Scheffler M (2001) Composition, structure and stability of RuO2(110) as a function of oxygen pressure. Phys Rev B 65:1–11CrossRefGoogle Scholar
  41. 41.
    Reuter K, Scheffler M (2003) Composition and structure of the RuO2(110) surface in an O2 and CO environment: implications for the catalytic formation of CO2. Phys Rev B 68:1–11CrossRefGoogle Scholar
  42. 42.
    Stull DR, Prophet H (1971) JANAF thermochemical tables, DTIC DocumentGoogle Scholar
  43. 43.
    Parkinson GS, Novotný Z, Jacobson P et al (2011) Room temperature water splitting at the surface of magnetite. J Am Chem Soc 133:12650–12655CrossRefPubMedGoogle Scholar

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

Authors and Affiliations

  1. 1.Key Laboratory for Green Chemical Technology of Ministry of Education, R&D Center for Petrochemical TechnologyTianjin UniversityTianjinPeople’s Republic of China
  2. 2.Collaborative Innovation Center of Chemical Science and EngineeringTianjinPeople’s Republic of China

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