Abstract
Mono and bicomponent TiO2 and WO3 nanoparticles were synthesized inside Vycor® glass pores, by cycles of impregnation of the glass with the respective oxide precursor followed by its thermal decomposition. The impregnation-decomposition cycle (IDC) methodology promoted a linear mass increase of the glass matrix, and allowed tuning the nanoparticle size. X-ray diffraction and Raman spectroscopy data allowed identifying the formation of TiO2 as anatase phase, while WO3 is a mixture of the γ-WO3 (monoclinic) and δ-WO3 (triclinic) phases. High resolution transmission electron microscopy images revealed that for 3, 5, and 7 IDC, the TiO2 nanoparticles obtained presented average diameters of 3.4, 4.3, and 5.1 nm, and the WO3 nanoparticles have 2.9, 4.6, and 5.7 nm sizes. These TiO2 and WO3 monocomponent nanoparticles were submitted to IDC with the other oxide precursor, resulting in bicomponent nanoparticles. The broadening and shift of the Raman bands related to titanium and tungsten oxides suggest the formation of hetero-structure core–shell nanoparticles with tunable core sizes and shell thicknesses.
References
Amadelli R, Samiolo L, Maldotti A, Molinari A, Valigi M, Gazzoli D (2008) Preparation, characterization, and photocatalytic behavior of Co-TiO2 with visible light response. Int J Photoenergy 1:1–9
Anpo M, Wada T, Kubokawa Y (1975) Photochemistry in the adsorbed layer. IV. Effects of oxygen upon the photolysis os the adsorbed alkylketones. Bull Chem Soc Jpn 48:2663–2666
Bersani D, Lottici PP, Ding XZ (1997) Phonon confinement effects in the Raman scattering by TiO2 nanocrystals. Appl Phys Lett 72:72–75
Bleuse J, Carayon S, Reiss P (2004) Optical properties of core/multishell CdSe/Zn(S, Se) nanocrystals. Physica E 21:331–335
Boulova M, Lucazeau G (2002) Crystallite nanosize effect on the structural transitions of WO3 studied by Raman spectroscopy. J Solid State Chem 167:425–434
Cangussu D, Nunes WC, Corrêa HLS, Macedo WAA, Knobel M, Alves OL, Souza Filho AG, Mazali IO (2009) γ-Fe2O3 nanoparticles dispersed in porous Vycor glass: a magnetically diluted integrated system. J Appl Phys 105:013901–013907
Carneiro NM, Nunes WC, Borges RP, Godinho M, Fernandez-Outon LE, Macedo WAA, Mazali IO (2010) NiO nanoparticles dispersed in mesoporous silica glass. J Phys Chem C 114:18773–18778
Cazzanelli E, Vinegoni C, Mariotto G, Kuzmin A, Purans J (1998) Low-temperature polymorphism in tungsten trioxide powders and its dependence on mechanical treatments. J Solid State Chem 143:24–32
Cazzanelli E, Papalino L, Pennisi A, Simone F (2001) Spatial variation of structural order in sputtered WO3 films. Electrochim Acta 46:1937–1944
Deepa M, Srivastava AK, Saxena TK, Agnihotry SA (2005) Annealing induced microstructural evolution of electrodeposited electrochromic tungsten oxide films. Appl Surf Sci 252:1568–1580
Di Fonzo F, Bailini A, Russo V, Baserga A, Cattaneo D, Beghi MG, Ossi PM, Casari CS, Li Bassi A, Bottani CE (2006) Synthesis and characterization of tungsten and tungsten oxide nanosstructured films. Catal Today 116:69–73
Elder SH, Cot FM, Su Y, Heald SM, Tyryshkin AM, Bowman MK, Gao Y, Joly AG, Balmer ML, Kolwaite AC, Magrini KA, Blake BM (2000) The discovery and study of nanocrystalline TiO2-(MoO3) core-shell materials. J Am Chem Soc 122:5138–5146
Frey GL, Rothschild A, Sloan J, Rosentsveig R, Popovitz-Biro R, Tenne R (2001) Investigations of nonstoichiometric tungsten oxide nanoparticles. J Solid State Chem 162:300–314
Gyorgy E, Socol G, Mihailescu IN, Ducu C, Ciuca S (2005) Structural and optical characterization of WO3 thin films for gas sensor applications. J Appl Phys 97:09327
Kansal SK, Singh M, Sud D (2008) Studies on TiO2/ZnO photocatalysed degradation of lignin. J Hazard Mater 153:412–417
Kim SK, Lee SW, Han JH, Lee B, Han S, Hwang CS (2010) Capacitors with an equivalent oxide thickness of <0.5 nm for nanoscale electronic semiconductor memory. Adv Funct Mater 20:2989–3003
Koma A (1999) Van der Waals epitaxy for highly lattice-mismatched systems. J Cryst Growth 201:236–241
Leghari SAK, Sajjad S, Chen F, Zhang J (2011) WO3/TiO2 composite with morphology change via hydrothermal template-free route as an efficient visible light photocatalyst. Chem Eng J 166:906–915
Lethy KJ, Beena D, Kumar RV, Pillai VPM, Ganesan V, Sathe V (2008) Structural, optical and morphological studies on laser ablated nanostructured WO3 thin films. Appl Surf Sci 254:2369–2376
Li S, El-Shall MS (1998) Synthesis of nanoparticles by reactive laser vaporization: silicon nanocrystals in polymers and properties of gallium and tungsten oxides. Appl Surf Sci 127:330–338
Lu G, Li X, Qu Z, Zhao Q, Li H, Shen Y, Chen G (2010) Correlations of WO3 species and structure with the catalytic performance of the selective oxidation of cyclopentane to glutaraldehyde on WO3/TiO2 catalysts. Chem Eng J 159:242–246
Mazali IO, Alves OL (2005) Characterization of nanosized TiO2 synthesized inside a porous glass-ceramic monolith by metallo-organic decomposition process. J Phys Chem Solids 66:37–46
Mazali IO, Souza Filho AG, Viana BC, Mendes Filho J, Alves OL (2006) Size-controllable synthesis of nanosized-TiO2 anatase using porous Vycor glass as template. J Nanopart Res 8:141–148
Mazali IO, Viana BC, Alves OL, Mendes Filho J, Souza Filho AG (2007) Structural and vibrational properties of CeO2 nanocrystals. J Phys Chem Solids 68:622–627
Menezes WG, Camargo PHC, Oliveira MM, Evans DJ, Soares JF, Zarbin AJG (2006) Sol-gel processing of a bimetallic alkoxide precursor confined in a porous glass matrix: a route to novel glass/metal oxide nanocomposites. J Colloid Interface Sci 299:291–296
Okubo T, Inoue H (1987) Surface diffusion on modified surface of porous glass. J Chem Eng 20:590–597
Park NG, Kang MG, Kim KM, Ryu KS, Chang SH (2004) Morphological and photoelectrochemical characterization of core-shell nanoparticle films for dye-sensitized solar cells: Zn-O type shell on SnO2 and TiO2 core. Langmuir 20:4246–4253
Powell G, Richens DT (1993) Complex formation and water exchange on the trinuclear dioxo-capped complexes [M3(μ3-O)2(μ-CH3CO2)6(OH2)3]2+ (M=Mo, W) and monooxo-capped complex [W3(μ3-O)(μ-CH3CO2)6(OH2)3]2+. Inorg Chem 32:4021–4029
Santos EB, Souza e Silva JM, Mazali IO (2010) Raman spectroscopy as a tool for elucidation of nanoparticles with core-shell structure of TiO2 and MoO3. Vib Spectrosc 54:89–92
Sauvet K, Sauques L, Rougier A (2010) Electrochromic properties of WO3 as a single layer and in a full device: from the visible to the infrared. J Phys Chem Solids 71:696–699
Straley C, Matteson A, Feng S, Schwartz LM, Kenyon WE, Banavar JR (1989) Magnetic resonance, digital image analysis, and permeability of porous media. Appl Phys Lett 51:1146–1148
Tan H, Xue JM, Shuter B, Li X, Wang J (2010) Synthesis of PEOlated Fe3O4@SiO2 nanoparticles via bioinspired silification for magnetic resonance imaging. Adv Funct Mater 20:722–731
Wang Q, Pan YZ, Huang SS, Ren ST, Li P, Li JJ (2011) Resistive and capacitive response of nitrogen-doped TiO2 nanotubes film humidity sensor. Nanotechnology 22:025501
Wijs GA, Boer PK, Groot RA, Kresse G (1999) Anomalous behavior of the semiconducting gap in WO3 from first-principles calculations. Phys Rev B 59:2684–2693
Xiao M, Wang L, Huang X, Wu Y, Dang Z (2009) Synthesis and characterization of WO3/titanate nanotubes nanocomposites with enhanced photocatalytic properties. J Alloys Compd 470:486–491
Yan A, Xie C, Zeng D, Cai S, Li H (2010) Synthesis, formation mechanism and illuminated sensing properties of 3D WO3 nanowall. J Alloys Compd 495:88–92
Yang XL, Dai WL, Guo C, Chen H, Cao Y, Li H, He H, Fan K (2005) Synthesis of novel core-shell structured WO3/TiO2 spheroids and its application in the catalytic oxidation of cyclopentene to glutaraldehyde by aqueous H2O2. J Catal 234:438–450
Acknowledgments
EBS and JMSS are indebted to Phd and FAPESP for Postdoctoral fellowships, respectively. FAS and IOM are indebted to CNPq and FAPESP for financial support and to Prof. C.H. Collins (IQ-UNICAMP, Brazil) for English revision. The Brazilian Synchrotron Light Laboratory (LNLS, Campinas-SP, Brazil) is also gratefully acknowledged for the XPD and HRTEM analysis. This is a contribution of the National Institute of Science and Technology in Complex Functional Materials (CNPq-MCT/FAPESP).
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de Barros Santos, E., de Souza e Silva, J.M., Sigoli, F.A. et al. Size-controllable synthesis of functional heterostructured TiO2–WO3 core–shell nanoparticles. J Nanopart Res 13, 5909–5917 (2011). https://doi.org/10.1007/s11051-011-0502-0
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DOI: https://doi.org/10.1007/s11051-011-0502-0