Skip to main content

Reduction Site in Ce n V m O k + Revealed by Gas Phase Thermal Desorption Spectrometry

Abstract

Vanadia supported on ceria shows particularly high catalytic reactivity. To elucidate its reduction site, cationic cerium-vanadium oxide clusters, Ce n V m O x + (n = 1–6, m = 0–5), were generated in the gas phase and their thermal response, such as reduction by oxygen release, was investigated by gas phase thermal desorption spectrometry. Stoichiometric and near-stoichiometric Ce n V m O x + clusters were dominantly formed, suggesting that Ce and V atoms in thermally stable clusters at 310 K have the oxidation states of + 4 and + 5, respectively. An oxygen molecule O2 was found to desorb from the clusters, resulting in formation of Ce n V m O x−2 +, upon heating. Presence of more than two Ce atoms in the clusters for odd values of m, or more than three Ce atoms for even values of m lowered the desorption temperature, indicating that not V atoms (+ 5 to + 4) but Ce atoms (+ 4 to + 3) in Ce n V m O x + tend to be reduced.

This is a preview of subscription content, access via your institution.

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

References

  1. Weckhuysen BM, Ketter DE (2003) Chemistry, spectroscopy and the role of supported vanadium oxides in heterogeneous catalysis. Catal Today 78:25–46

    CAS  Article  Google Scholar 

  2. Shah PR, Khader MM, Vohs JM, Gorte RJ (2008) A comparison of the redox properties of vanadia-based mixed oxides. J Phys Chem C 112:2613–2617

    CAS  Article  Google Scholar 

  3. Trovarelli A (1996) Catalytic properties of ceria and CeO2-containing materials. Catal Rev 38:439–520

    CAS  Article  Google Scholar 

  4. Skorodumova N, Simak S, Lundqvist BI, Abrikosov I, Johansson B (2002) Quantum origin of the oxygen storage capability of ceria. Phys Rev Lett 89:166601

    CAS  Article  Google Scholar 

  5. Jiang Y, Adams JB, Schilfgaarde MV, Sharma R, Crozier PA (2005) Theoretical study of environmental dependence of oxygen vacancy formation in CeO2. Appl Phys Lett 87:141917

    Article  Google Scholar 

  6. Wachs IE (2005) Recent conceptual advances in the catalysis science of mixed metal oxide catalytic materials. Catal Today 100:79–94

    CAS  Article  Google Scholar 

  7. Ganduglia-Pirovano MV, Popa C, Sauer J, Abbott H, Uhl A, Baron M, Stacchiola D, Bondarchuk O, Shaikhutdinov S, Freund HJ (2010) Role of ceria in oxidative dehydrogenation on supported vanadia catalysts. J Am Chem Soc 137:2345–2349

    Article  Google Scholar 

  8. Baron M, Abbott H, Bondarchuk O, Stacchiola D, Uhl A, Shaikhutdinov S, Freund HJ, Popa C, Ganduglia-Pirovano MV, Sauer J (2009) Resolving the atomic structure of vanadia monolayer catalysts: monomers, trimers, and oligomers on ceria. J Angew Chem Int Ed 48:8006–8009

    CAS  Article  Google Scholar 

  9. Da Silva JLF, Ganduglia-Pirovano MV, Sauer J (2007) Formation of the cerium orthovanadate CeVO4: DFT + U study. Phys Rev B 76:125117

    Article  Google Scholar 

  10. Jiang L, Wende T, Claes P, Bhattacharyya S, Sierka M, Meijer G, Leivens P, Sauer J, Asmis K (2011) Electron distribution in partially reduced mixed metal oxide systems: infrared spectroscopy of Ce m V n O o + gas-phase clusters. J Phys Chem A 115:11187–11192

    CAS  Article  Google Scholar 

  11. Koyama K, Kudoh S, Miyajima K, Mafuné F (2015) Dissociation energy for O2 release from gas-phase iron oxide clusters measured by temperature-programmed desorption experiments. Chem Phys Lett 625:104–109

    CAS  Article  Google Scholar 

  12. Mafuné F, Miyajima K, Morita K (2015) Release of oxygen from copper oxide cluster ions by heat and by reaction with NO. J Phys Chem C 119:11106–11113

    Article  Google Scholar 

  13. Nagata T, Miyajima K, Mafuné F (2015) Stable stoichiometry of gas-phase cerium oxide cluster ions and their reactions with CO. J Phys Chem A 119:1813–1819

    CAS  Article  Google Scholar 

  14. Koyama K, Kudoh S, Miyajima K, Mafuné F (2015) Stable stoichiometry of gas-phase manganese oxide cluster ions revealed by temperature-programmed desorption. J Phys Chem A 119:8433–8442

    CAS  Article  Google Scholar 

  15. Kurokawa H, Mafuné F (2016) Thermal desorption of oxygen from near-stoichiometric vanadium oxide cluster cation. Chem Phys Lett 651:24–27

    CAS  Article  Google Scholar 

  16. Masuzaki D, Nagata T, Mafuné F (2017) Desorption of oxygen from cationic niobium oxide clusters revealed by gas phase thermal desorption spectrometry and density functional theory calculations. J Phys Chem A 121:2079–2085

    CAS  Article  Google Scholar 

  17. Masuzaki D, Nagata T, Mafuné F (2017) Oxygen release from cationic niobium-vanadium oxide clusters, Nb n V m O k +, revealed by gas phase thermal desorption spectrometry and DFT calculations. J Phys Chem A 121:3864–3870

    CAS  Article  Google Scholar 

  18. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA et al (2013) Gaussian 09, revision E.01; Gaussian, Inc., Wallingford, CT

    Google Scholar 

  19. Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648

    CAS  Article  Google Scholar 

  20. Lee C, Yang W, Parr RG (1988) Development of the colle-salvetti correlation-energy formula into a functional of the electron density. Phys Rev B: Condens Matter Mater Phys 37:785

    CAS  Article  Google Scholar 

  21. Hay PJ, Wadt WR (1985) Ab initio effective core potentials for molecular calculations—potentials for K to Au including the outermost core orbitals. J Chem Phys 82:299–310

    CAS  Article  Google Scholar 

  22. Krishnan R, Binkley JS, Seeger R, Pople JA (1980) Self-consistent molecular orbital methods. XX. A basis set for correlated wave functions. J Chem Phys 72:650–654

    CAS  Article  Google Scholar 

  23. Glendening ED, Reed AE, Carpenter JE, Weinhold F, NBO, version 3.1

  24. Reed AE, Weinstock RB, Weinhold F (1985) Natural population analysis. J Chem Phys 83:735–746

    CAS  Article  Google Scholar 

  25. Ma JB, Meng JH, He S-G (2015) Gas-phase reaction of CeVO5 + cluster ions with C2H4: the reactivity of cluster bonded peroxides. Dalton Trans 44:3128–3135

    CAS  Article  Google Scholar 

  26. Boca R (1983) Dioxygen activation in transition metal complexes in the light of molecular orbital calculations. Coord Chem Rev 50:1–72

    CAS  Article  Google Scholar 

Download references

Acknowledgements

This work was supported by Grant-in-Aid for Challenging Exploratory Research (No. 26620002), for Young Scientists (B) (No. 17K14433), and for JSPS Fellows (No. 17J02017) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan (MEXT). The computations were partially performed using Research Center for Computational Science in Okazaki, Japan. T.N. is grateful for a JSPS Research Fellowship. The authors thank Dr. Ryuzo Nakanishi, Dr. Satoshi Takahashi and Dr. Ken Miyajima for helpful discussion.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Fumitaka Mafuné.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (PDF 397 KB)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Mafuné, F., Masuzaki, D. & Nagata, T. Reduction Site in Ce n V m O k + Revealed by Gas Phase Thermal Desorption Spectrometry. Top Catal 61, 42–48 (2018). https://doi.org/10.1007/s11244-017-0862-5

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11244-017-0862-5

Keywords

  • Cluster
  • Reduction
  • Thermal desorption spectrometry
  • Metal oxide
  • Oxidation state