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Electronic structure of the monoclinic and hexagonal trioxides of tungsten and hexagonal hydrogen tungsten bronze H0.24WO3

  • Physicochemical And Structural Investigations Of Materials
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Abstract

The methods of x-ray photoelectron spectroscopy (XPS) and x-ray emission spectroscopy (XES) were used to study the electronic structure of the monoclinic and hexagonal modifications of WO3, as well as hexagonal hydrogen tungsten bronze H0.24WO3. The OKα emission bands and the XPS spectra of the valence and core electrons were obtained for all of the compounds. It is shown that the half-width of the OKα bands and the XPS spectra of the valence electrons increase in the modification sequence WO3 → hexagonal WO3 → H0.24WO3. The near-Fermi region of the XPS valence-electron spectrum of the compound H0.24WO3 was found to contain an additional subband that is absent from both modifications of WO3. It was established that, within the experimental error, the binding energies of the W4f and O1s core electrons remain constant for all of the compounds that were studied.

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References

  1. H. J. Goldschmidt,Interstitial Alloys [Russian translation], Vol. 2, Mir, Moscow (1971).

    Google Scholar 

  2. W. L. Kehl, R. G. Hay, and D. Wahl, “The structure of tetragonal tungsten trioxide”,J. Appl. Phys.,23, No. 2, 212–215 (1952).

    Article  CAS  Google Scholar 

  3. S. Tanisaki, “On the phase transition of tungsten trioxide below room temperature,”J. Phys. Soc. Jpn.,15, No. 4, 566–573 (1960).

    Article  CAS  Google Scholar 

  4. B. O. Loopstra and H. M. Rietvald, “Further refinement of the structure of WO3,”Acta Cryst. B,25, No. 7, 1420–1421 (1969).

    Article  CAS  Google Scholar 

  5. E. Salje and K. Viswanathan, “Physical properties and phase transitions in WO3,”Acta Cryst. A,31, No. 3, 356–359 (1975).

    Article  Google Scholar 

  6. B. Gerand, G. Nowogrocki, J. Guenot, and M. Figlarz, “Structural study of a new hexagonal form of tungsten trioxide,”J. Solid State Chem.,29, No. 3, 429–434 (1979).

    Article  CAS  Google Scholar 

  7. B. Gerand, G. Nowogrocki, and M. Figlarz, “A new tungsten trioxide hydrate, WO3·1/3·H2O: Preparation, crystallization, and crystallographic study,”J. Solid State Chem.,38, No. 3, 312–320 (1981).

    Article  CAS  Google Scholar 

  8. M. Figlarz, B. Dumont, B. Gerand, and B. Beaudoin, “Etude de la transformation de phase WO3 hexagonal → WO3 monoclinique,”J. Microsc. Spectrosc. Electron.,7, No. 4, 371–386 (1982).

    CAS  Google Scholar 

  9. Yu. M. Solonin and Yu. G. Privalov, “Formation of hexagonal phases based on tungsten trioxide during the reduction of copper tungstate,”Dopov. Akad. Nauk Ukr. RSR, Ser. B, No. 1, 46–49 (1985).

    Google Scholar 

  10. N. Han, M. Hibino, and T. Kudo, “Synthesis of the hexagonal form of tungsten trioxide from peroxopolytungstate via ammonium paratungstate decahydrate,”Bull. Chem. Soc. Jpn.,71, 933–937 (1998).

    Article  CAS  Google Scholar 

  11. L. Kopp, B. N. Harmon, and S. H. Liu, “Band structure of cubic Na x WO3,”Solid State Commun.,22, No. 11, 677–679 (1977).

    Article  CAS  Google Scholar 

  12. D. W. Bullett, “A theoretical study of thex-dependence of the conduction-band density of states in metallic sodium tungsten bronzes Na x WO3,”Solid State Commun.,46, No. 7, 575–577 (1983).

    Article  CAS  Google Scholar 

  13. D. W. Bullett, “Bulk and surface electron states in WO3 and tungsten bronzes,”J. Phys. C: Solid State Phys.,16, No. 11, 2197–2207 (1983).

    Article  CAS  Google Scholar 

  14. A. Hjelm, C. G. Grandqvist, and J. M. Wills, “Electronic structure and optical properties of WO3, LiWO3, NaWO3, and HWO3,”Phys. Rev. B — Condens. Matter,54, No. 4, 2436–2445 (1996).

    Google Scholar 

  15. R. J. Colton and J. W. Rabalais, “Electronic structure of tungsten and some of its borides, carbides, nitrides, and oxides studied by x-ray electron spectroscopy,”Inorg. Chem.,15, No. 1, 236–238 (1976).

    Article  CAS  Google Scholar 

  16. J. Haber, J. Stoch, and L. Ungier, “Electron spectroscopic studies of the reduction of WO3,”J. Solid State Chem.,19, No. 2, 113–115 (1976).

    Article  CAS  Google Scholar 

  17. T. L. Barr, “An ESCA study of the termination of the passivation of elemental metals,”J. Chem. Phys.,82, No. 16, 1801–1810 (1978).

    Article  CAS  Google Scholar 

  18. V. I. Kruglov, E. P. Denisov, and S. L. Kraevskii, “Electronic structure of amorphous electrochromic films of tungsten trioxide and molybdenum trioxide,” in:Oxide Electrochromic Materials, A. Lusis (ed.) [in Russian], Izd. Latv. Gos. Univ., Riga (1981), pp. 66–85.

    Google Scholar 

  19. S. F. Ho, S. Contarini, and J. W. Rabalais, “Ion-beam-induced chemical changes in the oxyanions (MO n y ) and oxides (MO x ), where M=Cr, Mo, W, V, Nb, and Ta,”J. Phys. Chem.,91, No. 18, 4779–4788 (1987).

    Article  CAS  Google Scholar 

  20. B. A. De Angelis and M. Schiavello, “X-ray photoelectron spectroscopy of nonstoichiometric tungsten oxides,”J. Solid State Chem.,21, No. 1, 67–72 (1977).

    Article  Google Scholar 

  21. A. Meisel, G. Leonhardt, and R. Szargan,X-Ray Spectra and Chemical Binding, Springer-Verlag, Berlin; Heidelberg (1989).

    Google Scholar 

  22. E. A. Zhurakovsky and V. F. Nemchenko,Kinetic Properties and Electronic Structure of Interstitial Phases [in Russian], Nauk. Dumka, Kiev (1989).

    Google Scholar 

  23. V. V. Nemoshkalenko, V. N. Uvarov, and O. Ya. Yares’ko, “On the determination of atom charge states in oxides of 3d metals by the x-ray spectroscopy technique,”Met. Phys. Adv. Tech.,17, 289–301 (1998).

    Google Scholar 

  24. O. Yu. Khyzhun, “X-ray emission and photoelectron spectra of tungsten oxides,”Metallofiz. Nov. Tekh.,22, No. 3, 55–63 (2000).

    Google Scholar 

  25. O. Yu. Khyzhun, “Electronic structure of tungsten oxides,”Dopov. Nats. Akad. Nauk Ukraini, No. 7, 86–92 (1999).

  26. O. Yu. Khyzhun, “Effect of lattice defects and phase transformations on the electronic structure of compounds of 5d metals,”Physico-Mathematical Sciences Candidate Dissertation, Kiev (1992).

  27. O. Yu. Khyzhun, E. A. Zhurakovsky, A. K. Sinelnichenko, and V. A. Kolyagin, “Electronic structure of tantalum subcarbides studied by XPS, XES, and XAS methods,”J. Electron. Spectrosc. Relat. Phenom.,82, 179–192 (1996).

    Article  Google Scholar 

  28. M. V. Šušić and Yu. M. Solonin, “Thermic investigation of hexagonal hydrogen bronze, H x WO3,”J. Mater. Sci.,23, 267–271 (1988).

    Article  Google Scholar 

  29. K. Zigban, K. Nordling, A. Falman, et al.,Electron Spectroscopy [Russian translation], Mir, Moscow (1971).

    Google Scholar 

  30. V. I. Nefedov,X-Ray Electron Spectroscopy of Chemical Compounds. Handbook [in Russian], Khimiya, Moscow (1984).

    Google Scholar 

  31. O. Yu. Khyzhun, “XPS, XES, and XAS studies of the electronic structure of substoichiometric cubic TaC x and hexagonal Ta2C x carbides,”J. Alloys Comp.,259, 47–58 (1997).

    Article  CAS  Google Scholar 

  32. H. Höchst, R. D. Bringans, H. R. Shanks, and P. Steiner, “Failure of the rigid band model in Na x WO3: an XPS study,”Solid State Commun.,37, No. 1, 41–44 (1980).

    Article  Google Scholar 

  33. O. Yu. Khyzhun, E. A. Zhurakovsky, and Ya. V. Zaulichny, “Electronic structure of nonstoichiometric carbide W2C x in the homogeneous region,”Dopov. Akad. Nauk Ukr. SSR, Ser. A, No. 8, 62–65 (1989).

  34. O. Yu. Khyzhun, E. A. Zhurakovsky, and Ya. V. Zaulichny, “Electronic structure of nonstoichiometric tungsten carbides W2C x ,”Poroshk. Metall., No. 9, 77–83 (1990).

  35. O. Yu. Khyzhun, Ya. V. Zaulychny, and E. A. Zhurakovsky, “Electronic structure of tungsten and molybdenum germanides synthesized at high pressures,”J. Alloys Comp.,244, 107–112 (1996).

    Article  Google Scholar 

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Authors and Affiliations

  1. Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, Kiev

    O. Yu. Khyzhun & Yu. M. Solonin

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  1. O. Yu. Khyzhun
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  2. Yu. M. Solonin
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Translated from Poroshkovaya Metallurgiya, Nos. 5–6(413), pp. 82–91, May–June, 2000.

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Khyzhun, O.Y., Solonin, Y.M. Electronic structure of the monoclinic and hexagonal trioxides of tungsten and hexagonal hydrogen tungsten bronze H0.24WO3 . Powder Metall Met Ceram 39, 287–294 (2000). https://doi.org/10.1007/BF02684681

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  • DOI: https://doi.org/10.1007/BF02684681

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