Laboratory synthesis of microsheets of titanium dioxide from titanyl sulfate involves the use of ammonia solution, whereas another inorganic base is most likely to be employed at the industrial level, as ammonia is a toxic agent and therefore should be avoided according to European Union (EU) regulations. Selected nontoxic bases such as sodium, potassium, and lithium hydroxides have been tested as an alternative to ammonia solution to obtain amorphous and crystalline TiO2-based microsheets. The final products obtained at each step of the procedure (samples lyophilized and annealed at 230 and 800 °C) were analyzed with electron and atomic force microscopy, X-ray powder diffraction, thermal analysis, and Fourier transform infrared (FTIR) and Raman spectroscopies to determine their morphology and phase composition. The differences in the morphology of the obtained products were described in detail as well as phase and structural composition throughout the process. It was found that, in the last step of the synthesis, microsheets annealed at 800 °C were built of small rods and oval or platy crystalline particles depending on the base used. The temperature of formation of anatase, rutile, and alkali-metal titanates in correlation with the ionic radius of the alkali metal present in the sample was discussed.

Department of Chemistry University of Ostrava 30 dubna 22 701 03 Ostrava Czech Republic

Faculty of Chemistry Biological and Chemical Research Centre University of Warsaw Żwirki i Wigury 101 02 089 Warsaw Poland

Institute of Inorganic Chemistry of the Czech Academy of Sciences 250 68 Husinec Řež Czech Republic

Institute of Physics of the Czech Academy of Sciences Na Slovance 1999 2 182 21 Prague 8 Czech Republic

Zobrazit více v PubMed

Fujishima A.; Honda K. Electrochemical Photolysis of Water at a Semiconductor Electrode. Nature 1972, 238, 37–38. 10.1038/238037a0. PubMed DOI

Fujishima A.; Zhang X. T. Titanium dioxide photocatalysis: present situation and future approaches. C. R. Chim. 2006, 9, 750–760. 10.1016/j.crci.2005.02.055. DOI

Verma R.; Gangwar J.; Srivastava A. K. Multiphase TiO2 nanostructures: a review of efficient synthesis, growth mechanism, probing capabilities, and applications in bio-safety and health. RSC Adv. 2017, 7, 44199–44224. 10.1039/C7RA06925A. DOI

Zhang Y.; Wu L. Z.; Zeng Q. H.; Zhi J. F. An Approach for Controllable Synthesis of Different-Phase Titanium Dioxide Nanocomposites with Peroxotitanium Complex as Precursor. J. Phys. Chem. C 2008, 112, 16457–16462. 10.1021/jp804524y. DOI

Cong S.; Xu Y. Explaining the High Photocatalytic Activity of a Mixed Phase TiO2: A Combined Effect of O2 and Crystallinity. J. Phys. Chem. C 2011, 115, 21161–21168. 10.1021/jp2055206. DOI

Carp O.; Huisman C. L.; Reller A. Photoinduced reactivity of titanium dioxide. Prog. Solid State Chem. 2004, 32, 33–177. 10.1016/j.progsolidstchem.2004.08.001. DOI

Hanaor D.; Sorrell C. Review of the Anatase to Rutile Phase Transformation. J. Mater. Sci. 2011, 46, 855–874. 10.1007/s10853-010-5113-0. DOI

Chen X.; Mao S. S. Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications. Chem. Rev. 2007, 107, 2891–2959. 10.1021/cr0500535. PubMed DOI

Gupta S. M.; Tripathi M. A review on the synthesis of TiO2 nanoparticles by solution route. Cent. Eur. J. Chem. 2012, 10, 279–294. 10.2478/s11532-011-0155-y. DOI

Wang Y.; Lai Q.; Fan M. Review of the progress in preparing nano TiO2: An important environmental engineering material. J. Environ. Sci. 2014, 26, 2139.10.1016/j.jes.2014.09.023. PubMed DOI

Sun X.; Chen X.; Li Y. Large-Scale Synthesis of Sodium and Potassium Titanate Nanobelts. Inorg. Chem. 2002, 41, 4996–4998. 10.1021/ic0257827. PubMed DOI

Sasaki T.; Kooli F.; Iida M.; Michiue Y.; Takenouchi S.; Yajima Y.; Izumi F.; Chakoumakos B. C.; Watanabe M. A Mixed Alkali Metal Titanate with the Lepidocrocite-like Layered Structure. Preparation, Crystal Structure, Protonic Form, and Acid–Base Intercalation Properties. Chem. Mater. 1998, 10, 4123–4128. 10.1021/cm980535f. DOI

Masaki N.; Uchida S.; Yamane H.; Sato T. Characterization of a New Potassium Titanate, KTiO2(OH) Synthesized via Hydrothermal Method. Chem. Mater. 2002, 14, 419–424. 10.1021/cm0107427. DOI

Zhang X. C.; Li W.; Yang Z. Toxicology of nanosized titanium dioxide: an update. Arch. Toxicol. 2015, 89, 2207–2217. 10.1007/s00204-015-1594-6. PubMed DOI

Akple M.; Low J.; Qin Z.; Wageh S.; Al-Ghamdi A.; Yu J.; Liu S. Nitrogen-doped TiO2 microsheets with enhanced visible light photocatalytic activity for CO2 reduction. Chin. J. Catal. 2015, 36, 2127–2134. 10.1016/S1872-2067(15)60989-5. DOI

Deng A.; Zhu Y.; Guo X.; Zhou L.; Jiang Q. Synthesis of Various TiO2 Micro-/Nano-Structures and Their Photocatalytic Performance. Materials 2018, 11, 99510.3390/ma11060995. PubMed DOI PMC

Klementová M.; Motlochova M.; Bohacek J.; Kupcik J.; Palatinus L.; Plizingrova E.; Szatmary L.; Subrt J. Metatitanic Acid Pseudomorphs after Titanyl Sulfates: Nanostructured Sorbents and Precursors for Crystalline Titania with Desired Particle Size and Shape. Cryst. Growth Des. 2017, 17, 6762–6769. 10.1021/acs.cgd.7b01349. DOI

Bakardjieva S.; Caplovicova M.; Mamon F.; Fajgar R.; Jandova V.; Brovdyova T. Nanostructured TiO2 Microrods with 3D Nanovoids for Green Photocatalysis - PEC Water Splitting. Microsc. Microanal. 2019, 25, 2136–2137. 10.1017/S1431927619011413. DOI

Amarjargal A.; Tijing L. D.; Pant H. R.; Park C.-H.; Kim C. S. Simultaneous synthesis of TiO2 microrods in situ decorated with Ag nanoparticles and their bactericidal efficiency. Curr. Appl. Phys. 2012, 12, 1106–1112. 10.1016/j.cap.2012.02.003. DOI

Šubrt J.; Pulisova P.; Bohacek J.; Bezdicka P.; Plizingrova E.; Volfova L.; Kupcik J. Highly photoactive 2D titanium dioxide nanostructures prepared from lyophilized aqueous colloids of peroxo-polytitanic acid. Mater. Res. Bull. 2014, 49, 405–412. 10.1016/j.materresbull.2013.09.028. DOI

Selvamurugan M.; Hirankumar G.; Karuppuchamy S. Synthesis and characterization of nanostructured lithium titanate by simple peroxo route. J. Mater. Sci.: Mater. Electron. 2016, 27, 9699–9703. 10.1007/s10854-016-5031-2. DOI

Palkovská M.; Slovak V.; Subrt J.; Bohacek J.; Havlin J. Thermal decomposition of a peroxopolytitanic acid cryogel: TA/MS study. Thermochim. Acta 2017, 647, 1–7. 10.1016/j.tca.2016.11.009. DOI

Zhang Y.; Wu W.; Zhang K.; Liu C. H.; Yu A. F.; Peng M. Z.; Zhai J. Y. Raman study of 2D anatase TiO2 nanosheets. Phys. Chem. Chem. Phys. 2016, 18, 32178–32184. 10.1039/C6CP05496J. PubMed DOI

Masterton W. L.; Bolocofsky D.; Lee T. P. Ionic radii from scaled particle theory of the salt effect. J. Phys. Chem. A 1971, 75, 2809–2815. 10.1021/j100687a017. DOI

Shannon R.; Prewitt C. T. Effective Ionic Radii in Oxides and Fluorides. Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 1969, 25, 925–946. 10.1107/S0567740869003220. DOI

Yada M.; Goto Y.; Uota M.; Torikai T.; Watari T. Layered sodium titanate nanofiber and microsphere synthesized from peroxotitanic acid solution. J. Eur. Ceram. Soc. 2006, 26, 673–678. 10.1016/j.jeurceramsoc.2005.07.035. DOI

Motlochová M.; Slovak V.; Plizingrova E.; Klementova M.; Bezdicka P.; Subrt J. Thermal decomposition study of nanostructured amorphous lithium, sodium and potassium metatitanates. Thermochim. Acta 2018, 670, 148–154. 10.1016/j.tca.2018.10.028. DOI

Ryu Y.; Lee M.; Jeong E.; Kim H.; Jung W.; Baek S.; Lee G. D.; Park S.; Hong S.-S. Hydrothermal synthesis of titanium dioxides from peroxotitanate solution using different amine group-containing organics and their photocatalytic activity. Catal. Today 2007, 124, 88–93. 10.1016/j.cattod.2007.03.027. DOI

León A.; Reuquen P.; Garín C.; Segura R.; Vargas P.; Zapata P. A.; Orihuela P. FTIR and Raman Characterization of TiO2 Nanoparticles Coated with Polyethylene Glycol as Carrier for 2-Methoxyestradiol. Appl. Sci. 2017, 7, 4910.3390/app7010049. DOI

Bagheri S.; Kamyar S.; Abd Hamid S. B. Synthesis and Characterization of Anatase Titanium Dioxide Nanoparticles Using Egg White Solution via Sol-Gel Method. J. Chem. 2013, 84820510.1155/2013/848205. DOI

Azim Araghi M. E.; Shaban N.; Bahar M. Synthesis and characterization of nanocrystalline barium strontium titanate powder by a modified sol-gel processing. Mater. Sci.-Pol. 2016, 34, 63–68. 10.1515/msp-2016-0020. DOI

Zou J. A.; Gao J. C.; Xie F. Y. An amorphous TiO2 sol sensitized with H2O2 with the enhancement of photocatalytic activity. J. Alloys Compd. 2010, 497, 420–427. 10.1016/j.jallcom.2010.03.093. DOI

Moriguchi I.; Tsujigo Y.; Teraoka Y.; Kagawa S. Role of n-Octadecylacetoacetate as an Amphiphilic Chelating Agent in the Two-Dimensional Sol–Gel Synthesis of Ultrathin Films of Titania and Zirconia. J. Phys. Chem. B 2000, 104, 8101–8107. 10.1021/jp000484l. DOI

Shirpour M.; Cabana J.; Doeff M. New materials based on a layered sodium titanate for dual electrochemical Na and Li intercalation systems. Energy Environ. Sci. 2013, 6, 2538–2547. 10.1039/c3ee41037d. DOI

Mahadik M. A.; An G. W.; David S.; Choi S. H.; Cho M.; Jang J. S. Fabrication of A/R-TiO2 composite for enhanced photoelectrochemical performance: Solar hydrogen generation and dye degradation. Appl. Surf. Sci. 2017, 426, 833–843. 10.1016/j.apsusc.2017.07.179. DOI

Lan T.; Tang X.; Fultz B. Phonon anharmonicity of rutile TiO2 studied by Raman spectrometry and molecular dynamics simulations. Phys. Rev. B 2012, 85, 09430510.1103/PhysRevB.85.094305. DOI

Jo W. K.; Kumar S.; Isaacs M. A.; Lee A. F.; Karthikeyan S. Cobalt promoted TiO2/GO for the photocatalytic degradation of oxytetracycline and Congo Red. Appl. Catal., B 2017, 201, 159–168. 10.1016/j.apcatb.2016.08.022. DOI

Bamberger C. E.; Begun G. M. Sodium Titanates: Stoichiometry and Raman Spectra. J. Am. Ceram. Soc. 1987, 70, C-48–C-51. 10.1111/j.1151-2916.1987.tb04963.x. DOI

Bamberger C. E.; Begun G. M.; MacDougall C. S. Raman Spectroscopy of Potassium Titanates: Their Synthesis, Hydrolytic Reactions, and Thermal Stability. Appl. Spectrosc. 1990, 44, 30–37. 10.1366/0003702904085732. DOI

Liu X. Y.; Coville N. J. A Raman study of titanate nanotubes. S. Afr. J. Chem. 2005, 58, 110–115.

Zárate R. A.; Fuentes S.; Cabrera A.; Fuenzalida V. Structural characterization of single crystals of sodium titanate nanowires prepared by hydrothermal process. J. Cryst. Growth 2008, 310, 3630–3637. 10.1016/j.jcrysgro.2008.05.020. DOI

Zhang D. R.; Kim C. W.; Kang Y. S. A Study on the Crystalline Structure of Sodium Titanate Nanobelts Prepared by the Hydrothermal Method. J. Phys. Chem. C 2010, 114, 8294–8301. 10.1021/jp101482k. DOI

Pližingrová E.; Volfova L.; Svora P.; Labhsetwar N. K.; Klementova M.; Szatmary L.; Subrt J. Highly photoactive anatase foams prepared from lyophilized aqueous colloids of peroxo-polytitanic acid. Catal. Today 2015, 240, 107–113. 10.1016/j.cattod.2014.04.022. DOI

JCPDS PDF-4 Database; International Centre for Diffraction Data: Newtown Square, PA, 2019.

ICSD Database Fiz Karlsruhe, release 2019/1st ed.; Leibniz-Institut für Informationsinfrastruktur: Germany, 2019.

Study of Interactions between Titanium Dioxide Coating and Wood Cell Wall Ultrastructure