Journal of Molecular Modeling

, Volume 15, Issue 10, pp 1237–1244 | Cite as

Computational modeling of the adsorption and OH initiated photochemical and photocatalytic primary oxidation of nitrobenzene

Original Paper


The adsorption and primary oxidation step for the photodegradation of nitrobenzene (NB) have been studied computationally using MSINDO SCF MO method. The method performs efficiently for extended surface models such as Ti36O90H36. Molecular dynamics simulations have revealed that NB is linked to TiO2 surface at the titanium ion via the oxygen atoms of NO2 group. In addition, the computed vibrational density of states for the adsorbed NB molecule is in reasonably good agreement with the available experimental data and theoretical results. In order to identify the primary photochemical and photocatalytic OH initiated photooxidation intermediates, we have employed two different theoretical approaches, frontier orbital theory and Wheland localization theory. It has been found that the meta- hydroxynitrocyclohexadienyl radical is energetically more favored than para- and ortho-hydroxynitrocyclohexadienyl radicals for the photochemical photolysis, whereas in the case of photocatalysis, the OH radical attack is unselective and all three possible isomers have comparable stabilities.


Minimum energy adsorption conformation of nitrobenzene onto TiO2 (100) surface


Adsorption Model calculations Nitrobenzene Photooxidation Semiempirical method Titanium oxide 



One of the authors (H. S. Wahab) warmly thanks the Greek Ministry of Education and Religious Affairs for the award of a research fellowship and the International Institute of Education/SRF for supporting a postdoctoral stay. The work was partially supported by the Research Account of the University of Athens, under the grant KA: 70/4/6482.


  1. 1.
    Bhatkhande DS, Kamble SP, Sawant SB, Pangarkar VG (2004) Photocatalytic and photochemical degradation of nitrobenzene using artificial ultraviolet light. Chem Eng J 102:283–290CrossRefGoogle Scholar
  2. 2.
    Bhatkhande DS, Pangarkar VG, Beenackers AACM (2003) Photocatalytic degradation of nitrobenzene using titanium dioxide and concentrated solar radiation: chemical effects and scaleup. Water Res 37:1223–1230CrossRefGoogle Scholar
  3. 3.
    Palmisano G, Addamo M, Augugliaro V, Caronna T, Di Paola A, Lopez EG, Loddo V, Marci G, Palmesano L, Schiavello M (2007) Selectivity of hydroxyl radical in the partial oxidation of aromatic compounds in heterogeneous photocatalysis. Catal Today 122:118–127CrossRefGoogle Scholar
  4. 4.
    Priya MH, Madras GJ (2006) Photocatalytic degradation of nitrobenzenes with combustion synthesized nano-TiO2. Photochem Photobiol A: Chem 178:1–7CrossRefGoogle Scholar
  5. 5.
    Li QR, Gu CZ, Di Y, Yin H, Zhang JY (2006) Photodegradation of nitrobenzene using 172 nm excimer UV lamp. J Hazard Mater B 133:68–74CrossRefGoogle Scholar
  6. 6.
    Albarran G, Schuler RH (2005) Concerted effects of substituents in the reaction of OH radicals with aromatics: The cresols. J Phys Chem A 109:9363–9370CrossRefGoogle Scholar
  7. 7.
    Canle ML, Santaballa JA, Vulliet EJ (2005) On the mechanism of TiO2-photocatalyzed degradation of aniline derivatives. Photochem Photobiol A: Chem 175:192–200CrossRefGoogle Scholar
  8. 8.
    Turchi CS, Ollis DF (1990) Photocatalytic degradation of organic water contaminants: Mechanisms involving hydroxyl radical attack. J Catal 122:178–192CrossRefGoogle Scholar
  9. 9.
    Helz GR, Zepp RG, Crosby DG (1994) Aquatic and surface photochemistry. Lewis, Boca RatonGoogle Scholar
  10. 10.
    Ahlswede B, Jug K (1999) Consistent modifications of SINDO1: I. Approximations and parameters. J Comput Chem 20:563–571CrossRefGoogle Scholar
  11. 11.
    Ahlswede B, Jug K (1999) Consistent modifications of SINDO1: II. Applications to first- and second-row elements. J Comput Chem 20:572–578CrossRefGoogle Scholar
  12. 12.
    Bredow T, Geudtner G, Jug K (2001) MSINDO parameterization for third-row transition metals. J Comput Chem 22:861–887CrossRefGoogle Scholar
  13. 13.
    Zerner MC (1972) Removal of core orbitals in ‘valence orbital only’ calculations. Mol Phys 23:963–978CrossRefGoogle Scholar
  14. 14.
    Homann T, Bredow T, Jug K (2004) Adsorption of small molecules on the anatase (1 0 0) surface. Surf Sci 555:135–144CrossRefGoogle Scholar
  15. 15.
    Wahab HS, Bredow T, Aliwi SM (2008) Computational investigation of the adsorption and photocleavage of chlorobenzene on anatase TiO2 surfaces. Chem Phys 353:93–103CrossRefGoogle Scholar
  16. 16.
    Wahab HS, Bredow T, Aliwi SM (2008) MSINDO quantum chemical modeling study of water molecule adsorption at nano-sized anatase TiO2 surfaces. Chem Phys 354:50–57CrossRefGoogle Scholar
  17. 17.
    Shlyapochnikov VA, Khaikin LS, Grikina OE, Bock CW, Vilkov LV (1994) The structure of nitrobenzene and the interpretation of the vibrational frequencies of the C–NO2 moiety on the basis of ab initio calculations. J Mol Struct 326:1–16CrossRefGoogle Scholar
  18. 18.
    Wahab HS, Bredow T, Aliwi SM (2008) Computational modeling of the adsorption and photodegradation of 4-chlorophenol on anatase TiO2 particles. THEOCHEM 863:84–90CrossRefGoogle Scholar
  19. 19.
    Serpone N, Pelizzetti E (1989) Photocatalysis, fundamentals and applications. Wiley, New YorkGoogle Scholar
  20. 20.
    Zhang SJ, Jiang H, Li MJ, Yu HQ, Yin H, Li QR (2007) Kinetics and mechanisms of radiolytic degradation of nitrobenzene in aqueous solutions. Environ Sci Technol 41:1977–1982CrossRefGoogle Scholar
  21. 21.
    San N, Hatipoglu A, Koçtürk G, Çinar Z (2002) Photocatalytic degradation of 4-nitrophenol in aqueous TiO2 suspensions: Theoretical prediction of the intermediates. J Photochem Photobiol A: Chem 146:189–197CrossRefGoogle Scholar
  22. 22.
    Eberhardt MK, Yoshida M (1973) Radiation-induced homolytic aromatic substitution. I. Hydroxylation of nitrobenzene, chlorobenzene, and toluene. J Phys Chem 77:589–597CrossRefGoogle Scholar
  23. 23.
    Chen PC, Chieh YC, Tzeng SC (2003) Density functional calculations of the heats of formation for various aromatic nitro compounds. THEOCHEM 634:215–224CrossRefGoogle Scholar
  24. 24.
    Rodriguez M, Kirchner A, Contreras S, Chamarro E, Esplugas S (2000) Influence of H2O2 and Fe(III) in the photodegradation of nitrobenzene. J Photochem Photobiol A: Chem 133:123–127CrossRefGoogle Scholar
  25. 25.
    March J (1992) Advanced organic chemistry-reactions, mechanisms and structure, 4th edn. Wiley, New YorkGoogle Scholar

Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  1. 1.Laboratory of Physical Chemistry, Chemistry DepartmentNational and Kapodistrian University of AthensZografouGreece

Personalised recommendations