Abstract
A new facile method is proposed for the preparation of aqueous sols of highly crystalline tungsten trioxide with a particle size of 60–150 nm, containing no organic stabilizers/surfactants. These sols possess high sedimentation stability, which is quite unusual for inorganic colloidal systems containing relatively large particles, with a rather high density (ρ c(WO3) = 7.3 g/cm3). The method is based on the thermal decomposition of ammonium paratungstate, followed by dispersing the resulting powders in water under ultrasonic treatment. Thermal decomposition of ammonium paratungstate, and the composition and structure of the resulting tungsten trioxide and its aqueous dispersions, were investigated with thermal analysis combined with the mass spectrometry of gaseous thermolysis products, powder X-ray diffraction, scanning electron microscopy, low-temperature nitrogen adsorption, IR spectroscopy and dynamic light scattering. It has been demonstrated that the high sedimentation stability of WO3 results from electrostatic stabilization, which might be caused by the formation of tungstic acid on the surface of WO3 particles when they come into contact with water. The nanocrystalline WO3 obtained can be used to produce gas sensors for ammonia.
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Zheng H, Ou JZ, Strano MS, Kaner RB, Mitchell A, Kalantar-Zadeh K (2011) Nanostructured tungsten oxide—properties, synthesis, and applications. Adv Funct Mater 21:2175–2196
Michalak F, Rault L, Aldebert P (1992) Electrochromism with colloidal WO3 and IrO2. Opt Mater Technol Energy Eff Sol Energy Convers XI Chromogenics Smart Windows 1728:278–288
He T, Yao J (2007) Photochromic materials based on tungsten oxide. J Mater Chem 17:4547–4557
Bedja I, Hotchandani S, Kamat PV (1993) Photoelectrochemistry of quantized tungsten trioxide colloids: electron storage, electrochromic, and photoelectrochromic effects. J Phys Chem 97:11064–11070
Kalhori H, Ranjbar M, Salamati H, Coey JMD (2016) Flower-like nanostructures of WO3: fabrication and characterization of their in-liquid gasochromic effect. Sens Actuators B 225:535–543
Kamat PV, Vinodgopal K (1996) Sonochromic effect in WO3 colloidal suspensions. Langmuir 12:5739–5741
Yamazaki S, Yamate T, Adachi K (2013) Photocatalytic activity of aqueous WO3 sol for the degradation of orange II and 4-chlorophenol. Appl Catal A 454:30–36
Takeuchi M, Shimizu Y, Yamagawa H, Nakamuro T, Anpo M (2011) Preparation of the visible light responsive N3–doped WO3 photocatalyst by a thermal decomposition of ammonium paratungstate. Appl Catal B 110:1–5
Szilágyi IM, Fórizs B, Rosseler O, Szegedi Á, Németh P, Király P, Tárkányi G, Vajna B, Varga-Josepovits K, László K, Tóth AL, Baranyai P, Leskelä M (2012) WO3 photocatalysts: influence of structure and composition. J Catal 294:119–127
Nandiyanto ABD, Arutanti O, Ogi T, Iskandar F, Kim TO, Okuyama K (2013) Synthesis of spherical macroporous WO3 particles and their high photocatalytic performance. Chem Eng Sci 101:523–532
Alexander BD, Kulesza P, Rutkowska I, Solarska R, Augustynski J (2008) Metal oxide photoanodes for solar hydrogen production. J Mater Chem 18:2298–2303
Mansour SAA, Mohamed MA, Zaki MI (1988) Thermal decomposition and the creation of reactive solid surfaces. V. The genesis course of the WO3 catalyst from its ammonium paratungstate precursor. Thermochim Acta 129:187–196
Ross JRH (2012) Heterogeneous catalysis. Fundamentals and applications. Elsevier, Amsterdam
Siciliano T, Tepore A, Micocci G, Serra A, Manno D, Filippo E (2008) WO3 gas sensors prepared by thermal oxidization of tungsten. Sens Actuators B 133:321–326
Kim HJ, Lee JH (2014) Highly sensitive and selective gas sensors using p-type oxide semiconductors: overview. Sens Actuators B 192:607–627
Wetchakun K, Samerjai T, Tamaekong N, Liewhiran C, Siriwong C, Kruefu V, Wisitsoraat A, Tuantranont A, Phanichphant S (2011) Semiconducting metal oxides as sensors for environmentally hazardous gases. Sens Actuators B 160:580–591
Long H, Zeng W, Zhang H (2015) Synthesis of WO3 and its gas sensing: a review. J Mater Sci Mater Electron 26:4698–4707
Sawada S (1956) Thermal and electrical properties of tungsten oxide (WO3). J Phys Soc Jpn 11:1237–1246
Tilley RJD (1995) The crystal chemistry of the higher tungsten oxides. Int J Refract Met Hard Mater 13:93–109
Bartha L, Kiss AB, Szalay T (1995) Chemistry of tungsten oxide bronzes. Int J Refract Met Hard Mater 13:77–91
Vogt T, Woodward PM, Hunter BA (1999) The high-temperature phases of WO3. J Solid State Chem 144:209–215
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
Vaddiraju S, Chandrasekaran H, Sunkara MK (2003) Vapor phase synthesis of tungsten nanowires. J Am Chem Soc 125:10792–10793
Soultanidis N, Zhou W, Kiely CJ, Wong MS (2012) Solvothermal synthesis of ultrasmall tungsten oxide nanoparticles. Langmuir 28:17771–17777
Choi HG, Jung YH, Kim DK (2005) Solvothermal synthesis of tungsten oxide nanorod/nanowire/nanosheet. J Am Ceram Soc 88:1684–1686
Koltypin Y, Nikitenko SI, Gedanken A (2002) The sonochemical preparation of tungsten oxide nanoparticles. J Mater Chem 12:1107–1110
Contado C, Argazzi R (2011) Sedimentation field flow fractionation and flow field flow fractionation as tools for studying the aging effects of WO3 colloids for photoelectrochemical uses. J Chromatogr A 1218:4179–4187
Nenadovic MT, Rajh T, Micic OI, Nozik AJ (1984) Electron transfer reactions and flat-band potentials of tungsten(VI) oxide colloids. J Phys Chem 88:5827–5830
Sheng T, Chavvakula PP, Cao B, Yue N, Zhang Y, Zhang H (2014) Growth of ultra-long sodium tungsten oxide and tungsten oxide nanowires: effects of impurity and residue deposition. J Cryst Growth 395:61–67
Iwu KO, Galeckas A, Rauwel P, Kuznetsov AY, Norby T (2012) “One-dimensional WO3 and its hydrate: one-step synthesis, structural and spectroscopic characterization. J Solid State Chem 185:245–252
Zhang H, Duan G, Li Y, Xu X, Dai Z, Cai W (2012) Leaf-like tungsten oxide nanoplatelets induced by laser ablation in liquid and subsequent aging. Cryst Growth Des 12:2646–2652
Petrícek V, Dušek M, Palatinus L (2014) Crystallographic computing system JANA2006: general features. Z Krist 229:345–352
Saltykov SA (1976) Stereometricheskaya metallographiya (Stereometric metallography). Metallurgiya: Moscow, Russia. (In Russian)
Vander Voort GF (1984) Metallography: principles and practice. ASM International, New York
van Put JW, Verkroost TW, Sonneveld EJ (1990) X-ray powder diffraction data and unit cells of ammonium paratungstate tetrahydrate. Powder Diffr 5:167–169
Fait MJG, Lunk HJ, Feist M, Schneider M, Dann JN, Frisk TA (2008) Thermal decomposition of ammonium paratungstate tetrahydrate under non-reducing conditions. Characterization by thermal analysis, X-ray diffraction and spectroscopic methods. Thermochim Acta 469:12–22
Fait MJG, Moukhina E, Feist M, Lunk HJ (2016) Thermal decomposition of ammonium paratungstate tetrahydrate: new insights by a combined thermal and kinetic analysis. Thermochim Acta 637:38–50
French GJ, Sale FR (1981) A re-investigation of the thermal decomposition of ammonium paratungstate. J Mater Sci 16:3427–3436
Kalpakli AO, Arabaci A, Kahruman C, Yusufoglu I (2013) Thermal decomposition of ammonium paratungstate hydrate in air and inert gas atmospheres. Int J Refract Met Hard Mater 37:106–116
van Put JW (1995) Crystallisation and processing of ammonium paratungstate (APT). Int J Refract Met Hard Mater 13:61–76
Howard CJ, Stokes HT (2005) Structures and phase transitions in perovskites—a group-theoretical approach. Acta Cryst. A A61:93–111
Sawada S (1010) Thermal and electrical properties and crystal structure of tungsten oxide at high temperatures. Phys Rev 1953:91
Leute V (1966) Das Wolframtrioxid und seine Reaktion mit den Oxiden zweiwertiger Metalle. Z Phys Chem 48:307–318
Salje E (1977) The orthorhombic phase of WO3. Acta Cryst. B 33:574–577
Putnis A (2002) Mineral replacement reactions: from macroscopic observations to microscopic mechanisms. Min Mag 66:689–708
Rodriguez-Navarro C, Kudlacz K, Ruiz-Agudo E (2012) The mechanism of thermal decomposition of dolomite: new insights from 2D-XRD and TEM analyses. Am Mineral 97:38–51
Shukla AK, Ercius P, Gautam ARS, Cabana J, Dahmen U (2014) Electron tomography analysis of reaction path during formation of nanoporous NiO by solid state decomposition. Cryst Growth Des 14:2453–2459
Zaikovskii VI, Plyasova LM, Ziborov AV, Prudnikova OY, Yur’eva TM (1991) The thermal decomposition of zinc hydroxocarbonate. J Struct Chem 31:692–697
Diehl R, Brandt G, Salje E (1978) The crystal structure of triclinic WO3. Acta Crystallogr Sect B 34:1105–1111
Woodward PM, Sleight AW, Vogt T (1995) Structure refinement of triclinic tungsten trioxide. J Phys Chem Solids 56:1305–1315
Bevan DJM, Shelton JP, Anderson JS (1948) 351. Properties of some simple oxides and spinels at high temperatures. J Chem Soc 56:1305–1315
Merkle R, Maier J (2005) On the Tammann-rule. Z Anorg Allg Chemie 631:1163–1166
Perrin D (1969) Dissociation constants of inorganic acids and bases in aqueous solution. Pure Appl Chem 20:133–236
Cruywagen JJ (2000) Protonation, oligomerization, and condensation reactions of vanadate(V), molybdate(VI), and tungstate (VI). Adv Inorg Chem 49:127–182
Nakagawa I, Shimanouchi T (1964) Infrared absorption spectra of aquo complexes and the nature of co-ordination bonds. Spectrochim Acta 20:429–439
Kung MC, Kung HH (1985) IR studies of NH3, pyridine, CO, and NO adsorbed on transition metal oxides. Catal Rev 27:425–460
Rout CS, Hegde M, Govindaraj A, Rao CNR (2007) Ammonia sensors based on metal oxide nanostructures. Nanotechnology 18:205504
Gurlo A, Sahm M, Oprea A, Barsan N, Weimar U (2004) A p- to n-transition on α-Fe2O3-based thick film sensors studied by conductance and work function change measurements. Sens Actuators B 102:291–298
Wu Y-Q, Hu M, Wei X-Y (2014) A study of transition from n- to p-type based on hexagonal WO3 nanorods sensor. Chin Phys B. 23:40704
Acknowledgements
This work was supported by the Russian Science Foundation (Grant 16-13-10399). This research was performed using the equipment of the JRC PMR IGIC RAS.
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Shekunova, T.O., Baranchikov, A.E., Yapryntsev, A.D. et al. Ultrasonic disintegration of tungsten trioxide pseudomorphs after ammonium paratungstate as a route for stable aqueous sols of nanocrystalline WO3 . J Mater Sci 53, 1758–1768 (2018). https://doi.org/10.1007/s10853-017-1668-3
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DOI: https://doi.org/10.1007/s10853-017-1668-3