Skip to main content
SpringerLink
Log in

DFT studies of the adsorption and dissociation of H2O on the Al13 cluster: origins of this reactivity and the mechanism for H2 release

  • Original Paper
  • Published:
Journal of Molecular Modeling Aims and scope Submit manuscript

Abstract

A theoretical study of the chemisorption and dissociation pathways of water on the Al13 cluster was performed using the hybrid density functional B3LYP method with the 6-311+G(d, p) basis set. The activation energies, reaction enthalpies, and Gibbs free energy of activation for the reaction were determined. Calculations revealed that the H2O molecule is easily adsorbed onto the Al13 surface, forming adlayers. The dissociation of the first H2O molecule from the bimolecular H2O structure via the Grotthuss mechanism is the most kinetically favorable among the five potential pathways for O–H bond breaking. The elimination of H2 in the reaction of an H2O molecule with a hydrogen atom on the Al cluster via the Eley–Rideal mechanism has a lower activation barrier than the elimination of H2 in the reaction of two adsorbed H atoms or the reaction of OH and H. Following the adsorption and dissociation of H2O, the structure of Al13 is distorted to varying degrees.

Potential energy surface along the reaction coordinate for steps 5–9, calculated at the B3LYP/6-311+G(d,p) level

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Bruno C, Ingenito A, Cuoco F (2002) Using powdered aluminum for space propulsion. In: Proc 18th Int Workshop on Rocket Propulsion: Present and Future, Pozzuoli, Italy, 16–20 June 2002, pp 16–20

  2. Miller TF, Herr JD (2004) Green rocket propulsion by reaction of Al and Mg powders and water. In: 40th AIAA/ASME/SAE/ASEE Joint Propulsion Conf and Exhibition, Fort Lauderdale, FL, USA, 11–14 July 2004, paper 2004-4037

  3. Ingenito A, Bruno C (2004) Using aluminum for space propulsion. J Propuls Power 20:1056–1063

    Article  CAS  Google Scholar 

  4. Risha GA, Son SF, Yetter RA, Yang V, Tappan BC (2007) Combustion of nano-aluminum and liquid water. Proc Combust Inst 31:2029–2036

    Article  Google Scholar 

  5. Deng ZY, Zhu LL, Tang YB (2010) Role of particle sizes in hydrogen generation by the reaction of Al with water. J Am Ceram Soc 93:2998–3001

    Google Scholar 

  6. Muntyana SP, Volodinab GF, Grabkob DZ, Zhitar VF (2009) An aluminum alloy for generation of hydrogen from water. Surf Eng Appl Electrochem 45:347–351

    Article  Google Scholar 

  7. Diwan M, Hanna D, Shafirovich E, Varma A (2010) Combustion wave propagation in magnesium/water mixtures: experiments and model. Chem Eng Sci 65:80–87

    Article  CAS  Google Scholar 

  8. Kozin LF, Volkov SV, Goncharenko SG, Permyakov VV, Danil’tsev BI (2011) Kinetics and mechanism of interaction of aluminum and magnesium of Al–Mg–Bi ternary system with water. Prot Met Phys Chem Surf 47:171–180

    Article  CAS  Google Scholar 

  9. Levitas VI, Asay BW, Son SF, Pantoya M (2006) Melt dispersion mechanism for fast reaction of nanothermites. Appl Phys Lett 89:071909

    Article  Google Scholar 

  10. Roach PJ, Woodward WH, Castleman AW Jr, Reber AC, Khanna SN (2009) Complementary active sites cause size-selective reactivity of aluminum cluster anions with water. Science 23:492–495

    Article  Google Scholar 

  11. Reber AC, Khanna SN, Roach PJ, Woodward WH, Castleman AW Jr (2010) Reactivity of aluminum cluster anions with water: origins of reactivity and mechanisms for H2 release. J Phys Chem A 114:6071–6081

    Article  CAS  Google Scholar 

  12. Sun YL, Tian Y, Li SF (2008) Theoretical study on reaction mechanism of aluminum-water system. Chin J Chem Phys 21:245–249

    Article  CAS  Google Scholar 

  13. Ohmura S, Shimojo F, Kalia RK, Kunaseth M, Nakano A, Vashishta P (2011) Reaction of aluminum clusters with water J. Chem Phys 134:244702

    Google Scholar 

  14. Shimojo F, Ohmura S, Kalia RK, Nakano A, Vashishta P (2010) Molecular dynamics simulations of rapid hydrogen production from water using aluminum clusters as catalyzers. Phys Rev Lett 104:126102

    Article  Google Scholar 

  15. Álvarez-Barcia S, Flores JR (2009) The interaction of Al atoms with water molecules: a theoretical study. J Chem Phys 131:174307

    Article  Google Scholar 

  16. Oblath SB, Gole JL (1979) Aluminum hydration in the vapor-phase. J Chem Phys 70:581–582

    Article  CAS  Google Scholar 

  17. Kauffman JW, Hauge RH, Margrave JL (1980) Infrared matrix-isolation studies of the interactions and reactions of group IIIA metal atoms with water. J Am Chem Soc 102:6005–6011

    Article  Google Scholar 

  18. Russo MF Jr, Li R, Mench M, Duin ACT (2011) Molecular dynamic simulation of aluminum-water reactions using the ReaxFF reactive force field. Int J Hydrog Energy 36:5828–5835

    Article  CAS  Google Scholar 

  19. Wójcik A, Borowski T, Broclawik E (2011) The mechanism of the reaction of intradiol dioxygenase with hydroperoxy probe A DFT study. Catal Today 169:207–216

    Article  Google Scholar 

  20. Hadebe SW, Kruger HG, Robinson RS (2011) A DFT study of the hydroboration reaction with oxygen-, sulphur-, and nitrogen-based boranes. Comput Theor Chem 968:26–30

    Article  CAS  Google Scholar 

  21. Zhang ZG, Xu HG, Feng Y, Zheng WJ (2010) Investigation of the superatomic character of Al13 via its interaction with sulfur atoms. J Chem Phys 132:161103

    Article  Google Scholar 

  22. Tiwary AS, Mukherjee AK (2009) Mechanism of the CH3NH2–HNO2 reaction: ab initio DFT/TST study. J Mol Struct (THEOCHEM) 909:57–65

    Google Scholar 

  23. Meyer MP, Delmonte AJ, Singleton DA (1999) Reinvestigation of the isotope effects for the Claisen and aromatic Claisen rearrangements: the nature of the Claisen transition states. J Am Chem Soc 121:10865–10874

    Google Scholar 

  24. Ishida K, Morokuma K, Komornicki A (1977) The intrinsic reaction coordinate. An ab initio calculation for HNC to HCN and H−+CH4 to CH4+H−. J Chem Phys 66:2153–2156

    Google Scholar 

  25. Gonzalez C, Schlegel HB (1990) Reaction path following in mass-weighted internal coordinates. J Phys Chem 94:5523–5527

    Article  CAS  Google Scholar 

  26. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA et al (2003) Gaussian 03, revision C.02. Gaussian, Inc., Wallingford

  27. Wang LG, Kuklja MM (2010) First-principles study of small aluminum clusters: oxygen adsorptions, oxidation and phase stability. J Phys Chem Solid 71:140–144

    Google Scholar 

  28. Rao BK, Jena P (1999) Evolution of the electronic structure and properties of neutral and charged aluminum clusters: a comprehensive analysis. J Chem Phys 111:1890

    Article  CAS  Google Scholar 

  29. Cooper AS (1962) Precise lattice constants of germanium, aluminum, gallium arsenide, uranium, sulphur, quartz and sapphire. Acta Cryst 15:578–582

    Article  CAS  Google Scholar 

  30. Tougait O, Noel H (2004) Stoichiometry of UAl4. Intermetallics 12:219–223

    Article  CAS  Google Scholar 

  31. Jin S, Head JD (1994) Theoretical investigation of molecular water adsorption on the Al(111) surface. Surf Sci 318:204–216

    Google Scholar 

  32. Calvin MD, Head JD (1996) Theoretically modelling the water bilayer on the Al(111) surface using cluster calculations. Surf Sci 345:161–172

    Article  CAS  Google Scholar 

  33. Evans MG, Polanyi M (1935) Some applications of the transition state method to the calculation of reaction velocities, especially in solution. Trans Faraday Soc 31:875–894

    Article  CAS  Google Scholar 

  34. Winzor DJ, Jackson CM (2006) Interpretation of the temperature dependence of equilibrium and rate constants. J Mol Recognit 193:89–407

    Google Scholar 

  35. Laidler KJ, King MC (1983) The development of transition-state theory. J Phys Chem 87:2657–2664

    Article  CAS  Google Scholar 

  36. Sakai S (1992) Characterization of aluminum atom insertion mechanisms into fluorine–hydrogen, oxygen–hydrogen, nitrogen–hydrogen, chlorine–hydrogen, sulfur–hydrogen and phosphorus–hydrogen bonds by ab initio MO methods. J Phys Chem 96:8369–8373

    Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge the funding provided by the Laboratory of Science and Technology on Combustion and Explosion (grant no. 9140C35010201) for this work. J.Y.Z. thanks the Innovation Project for Postgraduates in Universities of Jiangsu Province (grant no. CXLX11_0246) for partial financial support.

Author information

Authors and Affiliations

  1. Key Laboratory of Soft Chemistry and Functional Materials of MOE, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, People’s Republic of China

    Jian-Ying Zhao & Xue-Hai Ju

  2. School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian, 223300, People’s Republic of China

    Jian-Ying Zhao

  3. Laboratory of Science and Technology on Combustion and Explosion, Xi’an Modern Chemistry Research Institute, Xi’an, 710065, People’s Republic of China

    Feng-Qi Zhao & Hong-Xu Gao

Authors
  1. Jian-Ying Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Feng-Qi Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hong-Xu Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xue-Hai Ju
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Xue-Hai Ju.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhao, JY., Zhao, FQ., Gao, HX. et al. DFT studies of the adsorption and dissociation of H2O on the Al13 cluster: origins of this reactivity and the mechanism for H2 release. J Mol Model 19, 1789–1799 (2013). https://doi.org/10.1007/s00894-012-1730-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00894-012-1730-7

Keywords

Search

Navigation