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Effect of titanium doping on the structure and reducibility of nanoparticle molybdenum dioxide

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Abstract

Molybdenum dioxide (MoO2) has potential not only in heterogeneous catalysis, but also as an electrode material in lithium-ion batteries and fuel cells. However, the reduction tendency to molybdenum metal is a limiting factor in the use of this oxide. In the present work, MoO2 was doped with Titanium (Ti4+) to increase the stability to reduction in a hydrogen-rich environment. Rather than using a conventional high-temperature solid-state reaction, a novel solution-based synthesis method followed by hydrothermal reduction was used. Nano-sized Ti-doped MoO2 particles with Ti/Mo atomic ratios of 0, 0.03, and 0.05 were prepared and characterized. X-ray and time-of-flight neutron powder diffraction (XRD and NPD) confirmed the presence of only the MoO2 phase. Transmission electron microscopy showed that the nanoparticles had an acicular morphology with particle sizes in the long dimension between 30 and 50 nm. Elemental mapping obtained by scanning electron microscopy with energy dispersive spectroscopy showed homogenous distribution of the dopant. Attenuated total reflectance-Fourier transform infrared spectroscopy revealed that the solubility limit of the synthesized Ti-doped MoO2 was reached at a Ti/Mo ratio of 0.05. This observation indicates that the bulk thermodynamic solubility limit can be exceeded at the nanoscale. X-ray photoelectron spectroscopy performed on 0.03 Ti-doped MoO2 samples showed that the Ti dopant is present as Ti4+ and the depth profile analysis indicated the presence of this species even in the bulk of the sample. This agrees with the data obtained from Rietveld refinement of the XRD and NPD results, which showed changes in the lattice parameters and Mo–Mo interatomic distance upon doping, suggesting a substitution of Mo4+ by Ti4+. The effect of Ti doping on the reducibility of MoO2 was demonstrated by in situ XRD in a hydrogen-rich environment.

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References

  • Aryanpour M, Hoffmann R, Di Salvo FJ (2009) Tungsten-doped titanium dioxide in the rutile structure: theoretical considerations. Chem Mater 21:1627–1635

    Article  Google Scholar 

  • Auborn JJ, Barberio YL (1987) Lithium intercalation cells without metallic lithium. J Electrochem Soc 134:638–641

    Article  Google Scholar 

  • Brodie I, Muray JJ (1992) The physics of micro/nano-fabrication. Plenum, New York

    Book  Google Scholar 

  • Burdett JK (1995) Structural-electronic relationships in rutile. Acta Cryst B51:547–558

    Article  Google Scholar 

  • Carter CB, Norton MG (2007) Ceramic materials: science and engineering. Springer, New York

    Google Scholar 

  • Chiorino A, Ghiotti G, Prinetto F, Carotta MC, Gnani D, Martinelli G (1999) Preparation and characterization of SnO2 and MoO x –SnO2 nanosized powders for thick film gas sensors. Sens Actuator B 58:338–349

    Article  Google Scholar 

  • Cotton FA (1966) Transition-metal compounds containing clusters of metal atoms. Q Rev Chem Soc 20:389–401

    Article  Google Scholar 

  • Dukstiene N, Sinkeviciute D, Guobiene A (2012) Morphological, structural and optical properties of MoO2 films electrodeposited on SnO2 glass plate. Cent Eur J Chem 10:1108–1118

    Article  Google Scholar 

  • Ellefson CA, Marin-Flores O, Ha S, Norton MG (2012) Synthesis and applications of molybdenum(IV) oxide. J Mater Sci 47:2057–2071

    Article  Google Scholar 

  • Griffith RH, Lindars PR (1950) Physical properties of promoted molybdenum catalysts. Nature 165:486–487

    Article  Google Scholar 

  • Hu WB, Li LP, Li GS, Tang CL, Sun L (2009) High-quality brookite TiO2 flowers: synthesis, characterization, and dielectric performance. Cryst Growth Des 9:3676–3682

    Article  Google Scholar 

  • Huq A, Hodges JP, Gourdon O, Heroux L (2011) Powgen: a third-generation high resolution high-throughput powder diffraction instrument at the spallation neutron source. Z Kristallogr Proc 1:127–135

    Google Scholar 

  • Huso J, Morrison JL, Hoeck H, Casey E, Bergman L, Pounds TD, Norton MG (2007) Low temperature LO-phonon dynamics of MgZnO nanoalloys. Appl Phys Lett 91:111906

    Article  Google Scholar 

  • Jacob KT, Shekhar C, Waseda Y (2008) Thermodynamic properties and phase diagram for the system MoO2–TiO2. J Am Ceram Soc 91:563–568

    Article  Google Scholar 

  • Katrib A, Mey D, Maire G (2001) Molybdenum and tungsten dioxides, XO2 (X = Mo, W), as reforming catalysts for hydrocarbon compounds. Catal Today 65:179–183

    Article  Google Scholar 

  • Kröger FA, Vink HJ (1956) Relations between the concentrations of imperfections in crystalline solids. Solid State Phys 3:307–435

    Google Scholar 

  • Kwon BW, Ellefson C, Breit J, Kim J, Norton MG, Ha S (2013) Molybdenum dioxide-based anode for solid oxide fuel cell application. J Power Sources 243:203–210

    Article  Google Scholar 

  • Larson AC, Von Dreele RB (2000) General structure analysis system (GSAS). Los Alamos National Lab Report LAUR 86-748

  • Lee JG, Mori H (2004) Direct evidence for reversible diffusional phase change in nanometer-sized alloy particles. Phys Rev Lett B 93:235501

    Article  Google Scholar 

  • Lee JG, Mori H, Yasuda H (2002) Alloy phase formation in nanometer-sized particles in the In-Sn system. Phys Rev B 65:132106

    Article  Google Scholar 

  • Liang Y, Tracy C, Weisbrod E, Fejes P, Theodore ND (2006) Effect of SiO2 incorporation on stability and work function of conducting MoO2. Appl Phys Lett 88:081901

    Article  Google Scholar 

  • Mahajan SS, Mujawar SH, Shinde PS, Inamdar AI, Patil PS (2009) Structural, morphological, optical and electrochemical properties of Ti-doped MoO3 thin films. Sol Energy Mat Sol Cells 93:183–187

    Article  Google Scholar 

  • Marin-Flores O, Ha S (2009) Activity and stability studies of MoO2 catalyst for the partial oxidation of gasoline. Appl Catal A 352:124–132

    Google Scholar 

  • Marin-Flores O, Scudiero L, Ha S (2009) X-ray diffraction and photoelectron spectroscopy studies of MoO2 as catalyst for partial oxidation of isooctane. Surf Sci 603:2327–2332

    Article  Google Scholar 

  • Marin-Flores O, Turba T, Ellefson C, Scudiero L, Breit J, Norton MG, Ha S (2010a) Nanoparticle molybdenum dioxide: a new alternative catalytic material for hydrogen production via partial oxidation of Jet-A fuels. J Nanoelectron Optoelectron 5:1–5

    Article  Google Scholar 

  • Marin-Flores O, Turba T, Ellefson C, Wang K, Breit J, Ahn J, Norton MG, Ha S (2010b) Nanoparticle molybdenum dioxide: a highly active catalyst for partial oxidation of aviation fuels. Appl Catal B Environ 98:186–192

    Article  Google Scholar 

  • Marin-Flores O, Turba T, Ellefson C, Scudiero L, Breit J, Norton MG, Ha S (2011) Sulfur poisoning of molybdenum dioxide during the partial oxidation of a Jet-A fuel surrogate. Appl Catal B Environ 105:61–68

    Article  Google Scholar 

  • Martos M, Morales J, Sánchez L (2002) Mechanochemical synthesis of Sn1−x Mo x O2 anode materials for Li-ion batteries. J Mater Chem 12:2979–2984

    Article  Google Scholar 

  • Merouani A, Amardjia-Adnani H (2008) Spectroscopic FT-IR study of TiO2 films prepared by sol–gel method. Int Sci J Altern Energy Ecol 6:151–154

    Google Scholar 

  • Nolan NT, Seery MK, Pillai SC (2009) Spectroscopic investigation of the anatase-to-rutile transformation of sol–gel-synthesized TiO2 photocatalysts. J Phys Chem C 113:16151–16157

    Article  Google Scholar 

  • Ouyang G, Tan X, Wang CX, Yang GW (2006) Solid solubility limit in alloying nanoparticles. Nanotechnology 17:4257–4262

    Article  Google Scholar 

  • Pankratz LB (1982) Thermodynamic properties of elements and oxides. U.S. Bureau of Mines Bulletin No. 672, U.S. Government Printing Office, Washington, DC

  • Pauling L (1960) The nature of the chemical bond, 3rd edn. Cornell University Press, Ithaca

    Google Scholar 

  • Prakash R, Phase DM, Choudhary RJ, Kumar R (2008) Structural, electrical and magnetic properties of Mo1−x Fe x O2 (x = 0–0.05) thin films grown by pulsed laser ablation. J Appl Phys 103:043712

    Article  Google Scholar 

  • Rogers DB, Shannon RD, Sleight AW, Gillson JL (1969) Crystal chemistry of metal dioxide with rutile related structures. Inorg Chem 8:841–849

    Article  Google Scholar 

  • Scanlon DO, Watson GW, Payne DJ, Atkinson GR, Egdell RG, Law DSL (2010) Theoretical and experimental study of the electronic structure of MoO3 and MoO2. J Phys Chem C 114:4636–4645

    Article  Google Scholar 

  • Schroeder T, Zegenhagen J, Magg N, Immaraporn B, Freund H-J (2004) Formation of a faceted MoO2 epilayer on Mo(112) studied by XPS, UPS and STM. Surf Sci 552:85–97

    Article  Google Scholar 

  • Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst A 32:751–767

    Article  Google Scholar 

  • Shi YF, Guo BK, Corr SA, Shi QH, Hu YS, Heier KR, Chen LQ, Seshadri R, Stucky GD (2009) Ordered mesoporous metallic MoO2 materials with highly reversible lithium storage capacity. Nano Lett 9:4215–4220

    Article  Google Scholar 

  • Sibu CP, Kumar SR, Mukundan P, Warrier KGK (2002) Structural modifications and associated properties of lanthanum oxide doped sol–gel nanosized titanium oxide. Chem Mater 14:2876–2881

    Article  Google Scholar 

  • Sutter EA, Sutter PW (2011) Giant carbon solubility in Au nanoparticles. J Mater Sci 46:7090–7097

    Article  Google Scholar 

  • Toby BH (2001) EXPGUI, a graphical user interface for GSAS. J Appl Cryst 34:210–213

    Article  Google Scholar 

  • West AR (1999) Basic solid state chemistry, 2nd edn. Wiley, Chichester

    Google Scholar 

  • Zhang JY, Boyd IW, O’Sullivan BJ, Hurley PK, Kelly PV, Sénateur JP (2002) Nanocrystalline TiO2 films studied by optical, XRD and FTIR spectroscopy. J Non-Cryst Solids 303:134–138

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Science Foundation (CBET1034308) and the Office of Naval Research (N00014-12-1-0830). Use of the Spallation Neutron Source is supported by the Division of Scientific User Facilities, Office of Basic Energy Sciences, U.S. Department of Energy.

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Authors and Affiliations

  1. School of Mechanical and Materials Engineering, Washington State University, Sloan Hall Room 201, 405 NE Spokane Street, Pullman, WA, 99164-2920, USA

    Qian He, Oscar Marin-Flores & M. Grant Norton

  2. The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA, 99164, USA

    Shuozhen Hu & Su Ha

  3. Chemistry Department and Materials Science and Engineering Program, Washington State University, Pullman, WA, 99164, USA

    Louis Scudiero

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  1. Qian He
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  2. Oscar Marin-Flores
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  5. Su Ha
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Correspondence to Qian He.

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He, Q., Marin-Flores, O., Hu, S. et al. Effect of titanium doping on the structure and reducibility of nanoparticle molybdenum dioxide. J Nanopart Res 16, 2385 (2014). https://doi.org/10.1007/s11051-014-2385-3

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  • DOI: https://doi.org/10.1007/s11051-014-2385-3

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