Abstract
Hydrous nanocrystalline zirconia was prepared from an unusual precursor—the bimetallic oxide zirconium tungstate (ZrW2O8)—in alkaline medium. Different experimental conditions (NaOH concentration, time and temperature) were used to investigate the effects on crystallographic, morphological, chemical and thermal characteristics of the products. The resulting materials are composed of particles with a crystal structure similar to that of cubic ZrO2 (or a mixture of tetragonal and cubic phases, depending on the synthesis conditions), with particle size around 5 nm and crystallites around 3 nm in diameter. These particles form high surface area agglomerates, exhibiting mesoporosity and capacity for adsorption of water and carbon dioxide. The synthesis mechanism appears to be constituted, first, by a chemical substitution reaction between the WO4 tetrahedra and hydroxyl ions, with subsequent solubilization of the structure. Indeed, excess hydroxyls in the medium form colloidal zirconium ions which polymerize/condense, generating crystalline nuclei in a process facilitated by heterogeneous nucleation and supersaturation. The presence of residual tungsten in all samples appears to be a key element for stabilizing the size and crystalline structure of the materials produced.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Aguila G, Guerrero S, Gracia F, Araya P (2006) Improvement of the thermal stability of hydrous zirconia by post-synthesis treatment with NaOH and NH4OH solutions. Appl Cat A-Gen 305(2):219–232. https://doi.org/10.1016/j.apcata.2006.03.025
Alario Franco MA, Sing KSW (1974) Propriedades químicas de superficie de los óxidos e hidróxidos de cromo. I. Adsorción de tetracloruro de carbon en el oxi-hidróxido ortorrómbico y sus productos de decomposición. An Quim 70:41–48
Antunes M (2016) Produção, dispersão e consolidação de zircônia obtida a partir do tunsgtato de zircônio. Doctoral Thesis. Pós-Graduação em Engenharia e Ciência dos Materiais – Universidade de Caxias do Sul, Caxias do Sul, 130 f
Bachiller-Baeza B, Rodriguez-Ramos I, Guerrero-Ruiz A (1998) Interaction of carbon dioxide with the surface of zirconia polymorphs. Langmuir 14(13):3556–3564. https://doi.org/10.1021/la970856q
Balzar D, Popa NC (2002) Improved modeling of residual strain/stress and crystallite-size distribution in Rietveld refinement. Adv X-ray Anal 45:152–157
Barrett EP, Joyner LG, Halenda PP (1951) The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. J Am Chem Soc 73(1):373–380. https://doi.org/10.1021/ja01145a126
Blesa MA, Maroto AJG, Passaggio SI, Figliolia NE, Rigotti G (1985) Hydrous zirconium dioxide: interfacial properties, the formation of monodisperse spherical particles, and its crystallization at high temperatures. J Mater Sci 20(12):4601–4609. https://doi.org/10.1007/BF00559350
Castro RHR, Marcos PJB, Lorriaux A, Steil MC, Gengembre L, Roussel P, Gouvea D (2008) Interface excess and polymorphic stability of nanosized zirconia-magnesia. Chem Mater 20(10):3505–3511. https://doi.org/10.1021/cm703599r
Chaplot SL (2005) Negative thermal expansion in ZrW2O8—do we give up the concept of normal mode? Curr Sci India 88:347–349
Chen C-W, Yang X-S, Chiang AST (2009) An aqueous process for the production of fully dispersible t-ZrO2 nanocrystals. J Ta Inst Chem Eng 40:296–301
Chitrakar R, Tesuka S, Sonoda A, Sakane K, Ooi K, Hirotsu T (2006) Selective adsorption of phosphate from seawater and wastewater by amorphous zirconium hydroxide. J Colloid Interf Sci 297(2):426–433. https://doi.org/10.1016/j.jcis.2005.11.011
Cho H-R, Walther C, Rothe J, Neck V, Denecke MA, Dardenne K, Fanghänel T (2005) Combined LIBD and XAFS investigation of the formation and structure of Zr(IV) colloids. Anal Bioanal Chem 383(1):28–40. https://doi.org/10.1007/s00216-005-3354-6
Chuah GK (1999) An investigation into the preparation of high surface area zirconia. Catal Today 49(1-3):131–139. https://doi.org/10.1016/S0920-5861(98)00417-9
Chuah GK, Jaenicke S (1997) The preparation of high surface area zirconia—influence of precipitating agent and digestion. Appl Catal A-Gen 163(1-2):261–273. https://doi.org/10.1016/S0926-860X(97)00103-8
Chuah GK, Jaenicke S, Pong BK (1998) The preparation of high-surface-area zirconia. II. Influence of precipitating agent and digestion on the morphology and microstructure of hydrous zirconia. J Catal 175(1):80–92. https://doi.org/10.1006/jcat.1998.1980
Clearfield A (1964) Crystalline hydrous zirconia. Inorg Chem 3(1):146–148. https://doi.org/10.1021/ic50011a034
Cortés-Jácome MA, Toledo-Antonio JA, Armendáriz H, Hernández I, Bokhimiz X (2002) Solid solutions of WO3 into zirconia in WO3-ZrO2 catalysts. J Solid State Chem 164(2):339–344. https://doi.org/10.1006/jssc.2001.9488
Daramola DA, Muthuvel M, Botte GG (2010) Density functional theory analysis of Raman frequency modes of monoclinic zirconium oxide using Gaussian basis sets and isotopic substitution. J Phys Chem B 114(29):9323–9329. https://doi.org/10.1021/jp9077135
Delhez R, de Keijser TH, Langford JI, Louër D, Mittemeijer EJ, Sonneved EJ (1993) Crystal imperfection broadening and peak shape in Rietveld method. In: Young RA (ed) The Rietveld method. Oxford University Press, New York, pp 147–148
Dell’Agli G, Colantuono A, Mascolo G (1999) The effect of mineralizers on the crystallization of zirconia gel under hydrothermal conditions. Solid State Ionics 123(1-4):87–94. https://doi.org/10.1016/S0167-2738(99)00109-5
Dell’Agli G, Mascolo G, Mascolo MC, Pagliuca C (2008) Drying effect on thermal behavior and structural modifications of hydrous zirconia gel. J Am Ceram Soc 91(10):3375–3379. https://doi.org/10.1111/j.1551-2916.2008.02635.x
Deshmane VG, Adewuyi YG (2012) Synthesis of thermally stable, high surface area, nanocrystalline mesoporous tetragonal zirconium dioxide (ZrO2): effects of different process parameters. Micropor Mesopor Mat 148(1):88–100. https://doi.org/10.1016/j.micromeso.2011.07.012
Djuraro E, Bouvier P, Lucazeau G (2000) Crystallite size effect on the tetragonal-monoclinic transition of undoped nanocrystalline zirconia studied by XRD and Raman spectrometry. J Solid State Chem 149(2):399–407. https://doi.org/10.1006/jssc.1999.8565
Gubanova NN, Baranchikov AY, Kopitsa GP, Almásy L, Angelov B, Yapryntsev AD, Rosta L, Ivanov VK (2015) Combined SANS and SAXS study of the action of ultrasound on the structure of amorphous zirconia gels. Ultrason Sonochem 24:230–237. https://doi.org/10.1016/j.ultsonch.2014.11.012
Hannink RHJ, Kelly PM, Muddle BC (2000) Transformation toughening in zirconia-containing ceramics. J Am Ceram Soc 83:461–487
Huang C, Tang Z, Zhang Z (2001) Differences between zirconium hydroxide (Zr(OH)4.nH2O) and hydrous zirconia (ZrO2.nH2O). J Am Ceram Soc 84:1637–1638
Jaenicke S, Chuah GK, Raju V, Nie YT (2008) Structural and morphological control in the preparation of high surface area zirconia. Catal Surv Jpn 12(3):153–169. https://doi.org/10.1007/s10563-008-9048-2
Jiao X, Chen D, Xiao L (2003) Effects of organic additives on hydrothermal zirconia nanocrystallites. J Cryst Growth 258(1-2):158–162. https://doi.org/10.1016/S0022-0248(03)01473-8
Kim B-K, Hamaguchi H-O (1997) Mode assignments of the Raman spectrum of monoclinic zirconia by isotopic exchange technique. Phys Status Solidi B 203(2):557–563. https://doi.org/10.1002/1521-3951(199710)203:2<557::AID-PSSB557>3.0.CO;2-C
Kobayashi T (2010) Solubility of zirconium and thorium in aqueous solutions containing organic acids. Master’s thesis. Kyoto University, Kyoto, 121 f
Köck E-M, Kogler M, Bielz T, Klötzer B, Penner S (2013) In situ FT-IR spectroscopic study of CO2 and CO adsorption on Y2O3, ZrO2, and yttria-stabilized ZrO2. J Phys Chem C 117(34):17666–17673. https://doi.org/10.1021/jp405625x
Langford JI, Louër D, Scardi P (2000) Effect of a crystallite size distribution on X-ray diffraction line profiles and whole-powder-pattern fitting. J Appl Crystallogr 33(3):964–974. https://doi.org/10.1107/S002188980000460X
Lara-García HA, Romero-Ibarra IC, Pfeiffer H (2014) Hierarchical Na-doped cubic ZrO2 synthesis by a simple hydrothermal route and its application in biodiesel production. J Solid State Chem 218:213–220. https://doi.org/10.1016/j.jssc.2014.06.040
Lind C (2012) Two decades of negative thermal expansion research: where do we stand? Materials 5(12):1125–1154. https://doi.org/10.3390/ma5061125
Manicone PF, Iommetti PR, Raffaelli L (2007) An overview of zirconia ceramics: basic properties and clinical applications. J Dent 35(11):819–826. https://doi.org/10.1016/j.jdent.2007.07.008
Marczewski AW (2002) A practical guide to isotherms of adsorption on heterogeneous surfaces. Available at: <http://adsorption.org/awm/ads/Ads.htm>. Access: April 20th, 2016
Marković JP, Milonjić SK (2006) Synthesis of zirconia colloidal dispersions by forced hydrolysis. J Serb Chem Soc 71:613–619
Matsui K, Ohgai M (2002) Formation mechanism of hydrous zirconia particles produced by hydrolysis of ZrOCl2 solutions. IV-effects of ZrOCl2 concentration and reaction temperature. J Am Ceram Soc 85:545–553
Mompean FJ, Perrone J, Illemassène M (Ed.) (2005) Chemical thermodynamics of zirconium. Elsevier, Amsterdam, volume 8
Morterra C, Orio L (1990) Surface characterization of zirconium oxide. II. The interaction with carbon dioxide at ambient temperature. Mater Chem Phys 24(3):247–268. https://doi.org/10.1016/0254-0584(90)90089-S
Nawrocki J, Rigney MP, McCormick A, Carr PW (1993) Chemistry of zirconia and its use in chromatography. J Chromatogr A 657(2):229–282. https://doi.org/10.1016/0021-9673(93)80284-F
Opalinska A, Malka I, Dzwolak W, Chudoba T, Presz A, Lojkowski W (2015) Size-dependent density of zirconia nanoparticles. Beilstein J Nanotech 6:27–35. https://doi.org/10.3762/bjnano.6.4
Palmer DA, Eldik RV (1983) The chemistry of metal carbonate and carbon dioxide complexes. Chem Rev 83(6):651–731. https://doi.org/10.1021/cr00058a004
Pan B, Xu J, Wu B, Li Z, Liu X (2013) Enhanced removal of fluoride by polystyrene anion exchanger supported hydrous zirconium oxide nanoparticles. Envir Sci Tech 47(16):9347–9354. https://doi.org/10.1021/es401710q
Patil KC, Hedge MS, Rattan T, Aruna ST (2008) Chemistry of nanocrystalline oxide materials: combustion synthesis, properties and applications. World Scientific Publishing, Singapura. https://doi.org/10.1142/6754
Perottoni CA (2000) Transições de fase em compostos de estrutura aberta sob altas pressões. Doctoral Thesis. Instituto de Física, Universidade Federal do Rio Grande do Sul, Porto Alegre. 177 f
Piskorz W, Grybos J, Zasada F, Cristol S, Paul J-F, Adamski A, Sojka Z (2011) Periodic DFT and atomistic thermodynamic modeling of the surface hydration equilibria and morphology of monoclinic ZrO2 nanocrystals. J Phys Chem C 115(49):24274–24286. https://doi.org/10.1021/jp2086335
Piskorz W, Grybos J, Zasada F, Zapala P, Cristol S, Paul J-F, Sojka Z (2012) Periodic DFT study of the tetragonal ZrO2 nanocrystals: equilibrium morphology modeling and atomistic surface hydration thermodynamics. J Phys Chem C 116(36):19307–19320. https://doi.org/10.1021/jp3050059
Pitcher MW, Ushakov SV, Navrotskyz A, Woodfield BF, Li G, Boerio-Goates J, Tissue BM (2005) Energy crossovers in nanocrystalline zirconia. J Am Ceram Soc 88:160–167
Pokrovski K, Jung KT, Bell AT (2001) Investigation of CO and CO2 adsorption on tetragonal and monoclinic zirconia. Langmuir 17(14):4297–4303. https://doi.org/10.1021/la001723z
Rouquerol F, Rouquerol J, Sing KSW, Llewellyn P, Maurin G (2014) Adsorption by powders and porous solids: principles, methodology and application, 2nd edn. Academic Press, Oxford
Ross-Medgaarden EI, Wachs IE (2007) Structural determination of bulk and surface tungsten oxides with UV-vis diffuse reflectance spectroscopy and Raman spectroscopy. J Phys Chem C 111(41):15089–15099. https://doi.org/10.1021/jp074219c
Shukla S, Seal S (2005) Mechanisms of room temperature metastable tetragonal phase stabilization in zirconia. Inter Mater Rev 50(1):45–64. https://doi.org/10.1179/174328005X14267
Silverstein RM, Bassler GC, Morrill TC (1991) Spectrometric identification of organic compounds, 5th edn. John Wiley & Sons, New York, pp 91–164
Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl Chem 57:603–619
Sing KSW, Williams RT (2005) Empirical procedures for the analysis of physisorption isotherms. Adsorpt Sci Technol 23(10):839–853. https://doi.org/10.1260/026361705777641990
Somavilla LM, Zorzi JE, Machado G, Ramos GR, de Amorim CLG, Perottoni CA (2011) Nanocrystalline hydrous zirconia from zirconium tungstate. J Am Ceram Soc 94(8):2640–2645. https://doi.org/10.1111/j.1551-2916.2011.04394.x
Song Y, Zhang J, Zhang Y, Zhou X, Wang J-A, Xu L (2011) Effect of crystallization mode of hydrous zirconia support on the isomerization activity of Pt/WO3-ZrO2. Catal Today 166(1):79–83. https://doi.org/10.1016/j.cattod.2010.06.002
Srinivasan R, Davis BH (1992) Influence of zirconium salt precursors on the crystal structures of zirconia. Catal Lett 14(2):165–170. https://doi.org/10.1007/BF00765230
Srinivasan R, Hubbard CR, Cavin B, Davis BH (1993) Factors determining the crystal phases of zirconia powders: a new outlook. Chem Mater 5(1):27–31. https://doi.org/10.1021/cm00025a009
Štefanić G, Štefanić II, Musić S (2000) Influence of the synthesis conditions on the properties of hydrous zirconia and the stability of low-temperature t-ZrO2. Mater Chem Phys 65(2):197–207. https://doi.org/10.1016/S0254-0584(00)00247-9
Stenina IA, Voropaeva EY, Veresov AG, Kapustin GI, Yaroslavtsev AB (2008) Effect of precipitation pH and heat treatment on the properties of hydrous zirconium dioxide. Russ J Inorg Chem 53(3):350–356. https://doi.org/10.1134/S0036023608030029
Stevens R (1986) Zirconia and zirconia ceramics, 2nd edn. Magnesium Elektron, Twickenham
Tahir MN, Gorgishvili L, Li J, Gorelik T, Kolb U, Nasdala L, Tremel W (2007) Facile synthesis and characterization of monocrystalline cubic ZrO2 nanoparticles. Solid State Sci 9(12):1105–1109. https://doi.org/10.1016/j.solidstatesciences.2007.07.033
Tai CY, Hsiao B-Y, Chiu H-Y (2004) Preparation of spherical hydrous-zirconia nanoparticles by low temperature hydrolysis in a reverse microemulsion. Colloids Surfaces A 237(1-3):105–111. https://doi.org/10.1016/j.colsurfa.2004.02.014
Tang X, Zheng X (2004) Raman scattering and t-phase lattice vibration of 3% (mole fraction) Y2O3-ZrO2. J Mater Sci Technol 20:485–489
Tsunekama S, Ito S, Kawazoe Y, Wang J-T (2003) Critical size of the phase transition from cubic to tetragonal in pure zirconia nanoparticles. Nano Lett 3(7):871–875. https://doi.org/10.1021/nl034129t
Vural Í (2011) Synthesis of zirconium tungstate and its use in composites with tunable thermal expansion coefficient. Master’s thesis. School of Natural and Applied Sciences, Middle East Technical University, Ankara, 149 f
Wang H, Li G, Xue Y, Li L (2007) Hydrated surface structure and its impacts on the stabilization of t-ZrO2. J Solid State Chem 180(10):2790–2797. https://doi.org/10.1016/j.jssc.2007.08.015
Acknowledgments
The authors acknowledge financial support from the Brazilian agencies Fundação de Amparo à Pesquisa do Rio Grande do Sul (FAPERGS), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, research grants #304831/2014-0 (CAP) and #304675/2015-6 (JEZ)), and Secretaria de Desenvolvimento Econômico, Ciência e Tecnologia do Estado do Rio Grande do Sul (SDECT). Thanks are due also to Netzsch Gerätebau GmbH, Fernanda Miotto (Universidade de Caxias do Sul), João Fiori and Rebecca Lewin (Bruker AXS GmbH) for X-ray microfluorescence analysis, and also to the staff of the Laboratório Central de Microscopia Professor Israel Baumvol (LCMic/UCS) and Instituto de Materiais Cerâmicos (IMC/UCS), particularly Robinson C. D. Cruz, Daniel Golle and Márcia Raquel H. Wendler, for technical assistance and helpful discussions.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Electronic supplementary material
ESM 1
Compositional images obtained by X-ray microfluorescence (Fig. S1), Raman spectra (Fig. S2), Gaussian fits of the mass spectrometric curves (Fig. S3 and Tables S1-S3), and the αs-plot used for the external area and microporous volume calculation based on nitrogen adsorption isotherms (Fig. S4). (DOCX 1343 kb)
Rights and permissions
About this article
Cite this article
Antunes, M., Perottoni, C.A., Gouvêa, D. et al. An investigation on the preparation of nanocrystalline hydrous zirconia from zirconium tungstate. J Nanopart Res 20, 25 (2018). https://doi.org/10.1007/s11051-017-4119-9
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-017-4119-9