Skip to main content
SpringerLink
Log in

Fluorolytic Sol-Gel Processes

  • Living reference work entry
  • First Online:
Handbook of Sol-Gel Science and Technology

Abstract

The nonaqueous fluorolytic sol-gel synthesis opens a very general and versatile access to nanoscopic metal fluorides. Based on MAS NMR, XRD, wide-angle X-ray powder diffraction (WAXS), and small-angle X-ray scattering (SAXS) investigations in combination with computational calculations, it is shown that a stepwise replacement of alkoxide by F-ions takes place resulting in the formation of a big variety of metal alkoxide fluoride clusters, some of them being isolated and structurally characterized. Nanoscopic metal fluorides obtained via this new synthesis approach exhibit distinctly different properties as compared with their classically prepared homologues. Optically fully transparent sols obtained this way can be used for the first time to manufacture antireflective coatings, corundum ceramics with drastically improved properties, as well as novel metal fluoride-based organic-inorganic composites. Metal fluoride xerogel powders obtained from such sols exhibit extremely strong Lewis acidity, but even metal hydroxide fluorides carrying both Lewis and Brønsted sites can be obtained. The properties of these new fluoride-based materials are presented and discussed in context with the abovementioned new fields of application.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution

Institutional subscriptions

References

  • Abraham A, Prins R, van Bokhoven JA, van Eck ERH, Kentgens APM. Multinuclear solid-state high-resolution and C-13 -{Al-27} double-resonance magic- angle spinning NMR studies on aluminum alkoxides. J Phys Chem B. 2006;110(13):6553–60.

    Article  Google Scholar 

  • Ahrens M, Scholz G, Braun T, Kemnitz E. Catalytic hydrodefluorination of fluoromethanes at room temperature by silylium-ion-like surface species. Angew Chem Int Ed Engl. 2013;52(20):5328–32.

    Article  Google Scholar 

  • Chupas PJ, Ciraolo MF, Hanson JC, Grey CP. In situ X-ray diffraction and solid-state NMR study of the fluorination of gamma-Al2O3 with HCF2Cl. J Am Chem Soc. 2001;123(8):1694–702.

    Article  Google Scholar 

  • Chupas PJ, Corbin DR, Rao VNM, Hanson JC, Grey CP. A combined solid-state NMR and diffraction study of the structures and acidity of fluorinated aluminas: implications for catalysis. J Phys Chem B. 2003;107(33):8327–36.

    Article  Google Scholar 

  • Dambournet D, Demourgues A, Martineau C, Durand E, Majimel J, Vimont A, Leclerc H, Lavalley JC, Daturi M, Legein C, Buzare JY, Fayon F, Tressaud A. Structural investigations and acidic properties of high surface area pyrochlore aluminium hydroxyfluoride. J Mater Chem. 2008a;18(21):2483–92.

    Article  Google Scholar 

  • Dambournet D, Demourgues A, Martineau C, Pechev S, Lhoste J, Majimel J, Vimont A, Lavalley JC, Legein C, Buzare JY, Fayon F, Tressaud A. Nanostructured aluminium hydroxyfluorides derived from beta-AlF3. Chem Mater. 2008b;20(4):1459–69.

    Article  Google Scholar 

  • Di Carlo L, Conte DE, Kemnitz E, Pinna N. Microwave-assisted fluorolytic sol–gel route to iron fluoride nanoparticles for Li-Ion batteries. Chem Commun. 2014;50(4):460–2.

    Article  Google Scholar 

  • Dimitrov A, Wuttke S, Troyanov S, Kemnitz E. Mg6F2(OMe)10(MeOH)14 – an alkoxide fluoride of an alkaline earth metal. Angew Chem Int Ed Engl. 2008;47(1):190–2.

    Article  Google Scholar 

  • Dimitrov A, Koch J, Troyanov SI, Kemnitz E. Aluminium alkoxide fluorides involved in the sol–gel synthesis of nanoscopic AlF3. Eur J Inorg Chem. 2009;35:5299–5301.

    Google Scholar 

  • Fedorov PP, Luginina AA, Kuznetsov SV, Osiko VV. Nanofluorides. J Fluor Chem. 2011;132(12):1012–39.

    Article  Google Scholar 

  • Feldmann C, Roming M, Trampert K. Polyol-mediated synthesis of nanoscale CaF2 and CaF2: Ce,Tb. Small. 2006;2(11):1248–50.

    Article  Google Scholar 

  • Fritz C. Inorganic–organic composite systems based on nanoscopic aluminium fluoride. Berlin Thesis: Humboldt-Universität zu Berlin; 2012.

    Google Scholar 

  • Fujihara S, Tada M, Kimura T. Controlling factors for the conversion of trifluoroacetate sols into thin metal fluoride coatings. J Sol–Gel Sci Technol. 2000;19(1-3):311–4.

    Article  Google Scholar 

  • Fujihara S, Kato T, Kimura T. Sol–gel processing and luminescent properties of rare-earth oxyfluoride materials. J Sol–Gel Sci Technol. 2003;26:953–6.

    Article  Google Scholar 

  • German Patent. 1994; EP 0 597 210 A1.

    Google Scholar 

  • Glaubitt W, Löbmann P. Antireflective coatings prepared by sol–gel processing: principles and applications. J Eur Ceram Soc. 2012;32(11):2995–9.

    Article  Google Scholar 

  • Guo Y, Wuttke S, Vimont A, Daturi M, Lavalley JC, Teinz K, Kemnitz E. Novel sol–gel prepared zinc fluoride: synthesis, characterisation and acid–base sites analysis. J Mater Chem. 2012;22(29):14587–93.

    Article  Google Scholar 

  • Guo Y, Gaczynski P, Becker K-D, Kemnitz E. Sol–gel synthesis and characterization of nanoscopic FeF3-MgF2 heterogeneous catalysts with bi-acidic properties. Chem Cat Chem. 2013;5:2223–32.

    Google Scholar 

  • Hegmann J, Löbmann P. Sol–gel preparation of TiO2 and MgF2 multilayers. J Sol-Gel Sci Technol. 2013;67(3):436–41.

    Article  Google Scholar 

  • Karg M, Scholz G, König R, Kemnitz E. Mechanistic insight into formation and changes of nanoparticles in MgF2 sols evidenced by liquid and solid state NMR. Dalton Trans. 2012;41:2360–6.

    Article  Google Scholar 

  • Kemnitz E. Nanoscale metal fluorides: a new class of heterogeneous catalysts. Catal Sci Technol. 2015;5:786–806.

    Article  Google Scholar 

  • Kemnitz E, Coman SM. Nanoscaled metal fluorides in heterogeneous catalysis. In: Parvulescu VI, Kemnitz E, editors. New materials for catalytic applications. Amsterdam: Elsevier BV; 2016. p. 133–87.

    Google Scholar 

  • Kemnitz E, Noack J. The non-aqueous fluorolytic sol–gel synthesis of nanoscaled metal fluorides. Dalton Trans. 2015;44:19411–31.

    Article  Google Scholar 

  • Kemnitz E, Scholz G. Sol–gel synthesis of metal fluorides: reactivity and mechanisms. In: Tressaud A, Groult H, Leroux F, editors. Modern synthetic routes and reactivity of fluorinated compounds. Amsterdam: Elsevier S&T; 2016.

    Google Scholar 

  • Kemnitz E, Groß U, Rüdiger S, Shekar CS. Amorphous metal fluorides with extraordinary high surface areas. Angew Chem Int Ed. 2003;42:4251–4.

    Article  Google Scholar 

  • Kemnitz E, Gross U, Rudiger S, Scholz G, Heidemann D, Troyanov SI, Morosov IV, Lemee-Cailleau MH. Comparative structural investigation of aluminium fluoride solvates. Solid State Sci. 2006;8(12):1443–52.

    Article  Google Scholar 

  • Kemnitz E, Scholz G, Rüdiger S. Sol–gel synthesis of nano-scaled metal fluorides – mechanism and properties. In: Tressaud A, editor. Functionalized inorganic fluorides. Hoboken: Wiley; 2010. p. 1–35.

    Chapter  Google Scholar 

  • Kemnitz E, Wuttke S, Coman SM. Tailor-made MgF2-based catalysts by sol–gel synthesis. Eur J Inorg Chem. 2011;4773–94.

    Google Scholar 

  • Kohl J, Wiedemann D, Nakhal S, Bottke P, Ferro N, Bredow T, Kemnitz E, Wilkening M, Heitjans P, Lerch M. Synthesis of ternary transition metal fluorides Li3MF6 via a sol–gel route as candidates for cathode materials in lithium-ion batteries. J Mater Chem. 2012;22(31):15819–27.

    Article  Google Scholar 

  • König R. Magnetresonanzuntersuchungen zur Ausbildung lokaler Strukturen bei der Sol–gel Synthese von Aluminiumalkoxidfluorid. Berlin Thesis: Humboldt-Universität zu Berlin; 2006.

    Google Scholar 

  • König R, Scholz G, Thong NH, Kemnitz E. Local structural changes at the formation of fluoride sols and gels: a mechanistic study by multinuclear NMR spectroscopy. Chem Mater. 2007;19(9):2229–37.

    Article  Google Scholar 

  • König R, Scholz G, Bertram R, Kemnitz E. Crystalline aluminium hydroxy fluorides – suitable reference compounds for F-19 chemical shift trend analysis of related amorphous solids. J Fluor Chem. 2008a;129(7):598–606.

    Article  Google Scholar 

  • König R, Scholz G, Pawlik A, Jäger C, van Rossum B, Oschkinat H, Kemnitz E. Crystalline aluminum hydroxy fluorides: structural insights obtained by high field solid state NMR and trend analyses. J Phys Chem C. 2008b;112(40):15708–20.

    Article  Google Scholar 

  • König R, Scholz G, Pawlik A, Jäger C, van Rossum B, Kemnitz E. Identification of AlFx(OR)y species in strongly disordered aluminium isopropoxide fluoride solids: a field-dependent MAS NMR study. J Phys Chem C. 2009a;113:15576–85.

    Article  Google Scholar 

  • König R, Scholz G, Kemnitz E. Local structural changes in aluminium isopropoxide fluoride xerogels and solids as a consequence of the progressive fluorination degree. J Phys Chem C. 2009b;113:6426–38.

    Article  Google Scholar 

  • König R, Scholz G, Kemnitz E. The fluorolytic sol–gel reaction of aluminium alkoxides: a multinuclear MAS NMR study of structural influences of the synthesis parameters. J Sol–Gel Sci Technol. 2010;56(2):145–56.

    Article  Google Scholar 

  • König R, Scholz G, Veiczi M, Jäger C, Troyanov SI, Kemnitz E. New crystalline aluminium alkoxide fluorides: evidence of the mechanism of the fluorolytic sol–gel reaction. Dalton Trans. 2011;40:8701–10.

    Article  Google Scholar 

  • Krahl T, Kemnitz E. Amorphous aluminium bromide fluoride. Angew Chem Int Ed. 2004;43;6553–6.

    Article  Google Scholar 

  • Krahl T, Kemnitz E. The very strong Lewis acids aluminium chlorofluoride (ACF) and bromofluoride (ABF) – synthesis, structure, and Lewis acidity. J Fluorine Chem. 2006;127:663–78.

    Article  Google Scholar 

  • Krahl T, Stösser R, Kemnitz E, Scholz G, Feist M, Silly G, Buzaré JY. New structutral insides into alumniumchlorofluoride. Inorg Chem. 2003;42:6474–83.

    Article  Google Scholar 

  • Krahl T, Vimont A, Eltanany G, Daturi M, Kemnitz E. Determination of the acidity of high surface AlF3 by IR spectroscopy of adsorbed CO probe molecules. J Phys Chem C. 2007;111(49):18317–25.

    Article  Google Scholar 

  • Krahl T, Broßke D, Scheurell K, Lintner B, Kemnitz E. Novel aspects in the chemistry of the non-aqueous fluorolytic sol–gel synthesis of nanoscaled homodisperse MgF2 sols for antireflective coatings. J Mater Chem C. 2016;4:1454–1466.

    Google Scholar 

  • Krüger H, Kemnitz E, Hertwig A, Beck U. Transparent MgF2-films by sol–gel coating: synthesis and optical properties. Thin Solid Films. 2008a;516:4175–7.

    Article  Google Scholar 

  • Krüger H, Kemnitz E, Hertwig A, Beck U. Moderate temperature sol–gel deposition of magnesium fluoride films for optical UV-applications: a study on homogeneity using spectroscopic ellipsometry. Phys Status Solidi A. 2008b;205:821–4.

    Article  Google Scholar 

  • Mosiadz M, Juda NL, Hopkins SC, Soloducho J, Glowacki BA. An in-depth in situ IR study of the thermal decomposition of barium trifluoroacetate hydrate. Thermochim Acta. 2011;513(1-2):33–7.

    Article  Google Scholar 

  • Murata T, Ishizawa H, Motoyama I, Tanaka A. Investigations of MgF2 optical thin films prepared from autoclaved. J Sol–Gel Sci Technol. 2004;32:161–5.

    Article  Google Scholar 

  • Murthy JK, Gross U, Rüdiger S, Rao VV, Kumar VV, Wander A, Bailey CL, Harrison NM, Kemnitz E. Aluminum chloride as a solid is not a strong Lewis acid. J Phys Chem B. 2006;110(16):8314–9.

    Article  Google Scholar 

  • Nandiyanto ABD, Iskandar F, Ogi T, Okuyama K. Nanometer to submicrometer magnesium fluoride particles with controllable morphology. Langmuir. 2010;26(14):12260–6.

    Article  Google Scholar 

  • Noack J, Schmidt L, Gläsel H-J, Bauer M, Kemnitz E. Inorganic–organic nanocomposites based on sol–gel derived magnesium fluoride. Nanoscale. 2011a;3:4774–9.

    Article  Google Scholar 

  • Noack J, Emmerling F, Kirmse H, Kemnitz E. Sols of nanosized magnesium fluoride: formation and stabilisation of nanoparticles. J Mater Chem. 2011b;21:15015–1521.

    Article  Google Scholar 

  • Noack J, Scheurell K, Kemnitz E, Garcia-Juan P, Rau H, Lacroix M, Eicher J, Lintner B, Sontheimer T, Hofmann T, Hegmann J, Jahn R, Löbmann P. MgF2 antireflective coatings by sol–gel processing: film preparation and thermal densification. J Mater Chem. 2012;22:18535–41.

    Article  Google Scholar 

  • Noack J, Fritz C, Flügel C, Hemmann F, Gläsel HJ, Kahle O, Dreyer C, Bauer M, Kemnitz E. Metal fluoride-based transparent nanocomposites with low refractive indices. Dalton Trans. 2013;42(16):5706–10.

    Article  Google Scholar 

  • Palashov OV, Khazanov EA, Mukhin IB, Mironov IA, Smirnov AN, Dukel’skii KV, Fedorov PP, Osiko VV, Basiev TT. Comparison of the optical parameters of a CaF2 single crystal and optical ceramics. Quantum Electron. 2007;37(1):27–8.

    Article  Google Scholar 

  • Pilvi T, Hatanpaa T, Puukilainen E, Arstila K, Bischoff M, Kaiser U, Kaiser N, Leskela M, Ritala M. Study of a novel ALD process for depositing MgF2 thin films. J Mater Chem. 2007;17(48):5077–83.

    Article  Google Scholar 

  • Pilvi T, Puukilainen E, Kreissig U, Leskela M, Ritala M. Atomic layer deposition of MgF2 thin films using TaF5 as a novel fluorine source. Chem Mater. 2008;20(15):5023–8.

    Article  Google Scholar 

  • Raut HK, Dinachali SS, Ansah-Antwi KK, Ganesh VA, Ramakrishna S. Fabrication of highly uniform and porous MgF anti-reflective coatings by polymer-based sol–gel processing on large-area glass substrates. Nanotechnology. 2013;24:505201.

    Article  Google Scholar 

  • Rehmer A, Scheurell K, Kemnitz E. Formation of nanoscopic CaF2 via a fluorolytic sol–gel process for antireflective coatings. J Mater Chem C. 2015;3:1716–23.

    Article  Google Scholar 

  • Ritter B, Krahl T, Rurack K, Kemnitz E. Nanoscale CaF2 doped with Eu3+ and Tb3+ through fluorolytic sol–gel synthesis. J Mater Chem C. 2014;2:8607–13.

    Article  Google Scholar 

  • Rüdiger S, Kemnitz E. The fluorolytic sol–gel route to metal fluorides – a versatile process opening a variety of application fields. Dalton Trans. 2008;9:1117–1127.

    Google Scholar 

  • Rüdiger S, Groß U, Feist M, Prescott H, Shekar CS, Troyanov SI, Kemnitz E. Non-aqueous synthesis of high surface area aluminium fluoride – a mechanistic investigation. J Mater Chem. 2005;15:588–97.

    Article  Google Scholar 

  • Rüdiger S, Gross U, Kemnitz E. Non-aqueous sol–gel synthesis of nano-structured metal fluorides. J Fluor Chem. 2007;128(4):353–68.

    Article  Google Scholar 

  • Rywak AA, Burlitch JM. Sol–gel synthesis of nanocrystalline magnesium fluoride: its use in the preparation of MgF2 films and MgF2-SiO2 composites. Chem Mater. 1996;8(1):60–7.

    Article  Google Scholar 

  • Scheurell K, König R, Troyanov SI, Kemnitz E. Structural chemistry of magnesium acetates. Z Anorg Allg Chem. 2012;638:1265–73.

    Article  Google Scholar 

  • Scheurell K, Noack J, König R, Hegmann J, Jahn R, Hofmann T, Löbmann P, Lintner B, Garcia-Juan P, Eicher J, Kemnitz E. Optimization of a sol–gel synthesis route for the preparation of MgF2 particles for a large scale coating process. Dalton Trans. 2015a;44:19501–8.

    Article  Google Scholar 

  • Scheurell K, Kemnitz E, Garcia-Juan P, Eicher J, Lintner B, Hegmann J, Jahn R, Hofmann T, Löbmann P. Porous MgF2 antireflextive λ/4 films prepared by sol–gel processing: comparison of synthesis approaches. J Sol–Gel Sci Technol. 2015b;76:82–9.

    Article  Google Scholar 

  • Schmidt L, Dimitrov A, Kemnitz E. A new approach to prepare nanoscopic rare earth metal fluorides: the fluorolytic sol–gel synthesis of ytterbium fluoride. Chem Commun. 2014a;50(50):6613–6.

    Article  Google Scholar 

  • Schmidt L, Emmerling F, Kirmse H, Kemnitz E. Sol–gel synthesis and characterisation of nanoscopic strontium fluoride. RSC Adv. 2014b;4:32–8.

    Article  Google Scholar 

  • Scholz G, Brehme S, König R, Heidemann D, Kemnitz E. Crystalline aluminum hydroxide fluorides AlFx(OH)(3-x)center dot H2O: structural Insights from and H-2 solid state NMR and vibrational spectroscopy. J Phys Chem C. 2010;114(23):10535–43.

    Article  Google Scholar 

  • Scholz G, Stosiek C, Noack J, Kemnitz E. Local fluorine environments in nanoscopic magnesium hydr(oxide) fluorides studied by 19F MAS NMR. J Fluorine Chem. 2011;132:1079–85.

    Article  Google Scholar 

  • Sevonkaev I, Matijevic E. Formation of magnesium fluoride particles of different morphologies. Langmuir. 2009;25(18):10534–9.

    Article  Google Scholar 

  • Stosiek C, Ludwig H, Reichel U, Scholz G, Kemnitz E. Nanoscopic metal fluorides as promising sintering aids for high-performance alumina ceramics. J Ceram Sci Technol. 2011;2(1):31–8.

    Google Scholar 

  • Sun XY, Gu M, Huang SM, Jin XJ, Liu XL, Liu B, Ni C. Luminescence Behavior of Tb3+ ions in transparent glass and glass-ceramics containing CaF2 nanocrystals. J Lumin. 2009;129(8):773–7.

    Article  Google Scholar 

  • Tada M, Fujihara S, Kimura T. Sol–gel processing and characterization of alkaline earth and rare-earth fluoride thin films. J Mater Res. 1999;14(4):1610–6.

    Article  Google Scholar 

  • Tressaud A, editor. Functionalized inorganic fluorides: synthesis, characterization and properties of nanostructured solids. Hoboken: Wiley; 2010.

    Google Scholar 

  • US-Patent. 2011. US20110122497A1.

    Google Scholar 

  • US-Patent. 2014. US20140147594A1.

    Google Scholar 

  • Wang JS, Miao WR, Li YX, Yao HC, Li ZJ. Water-soluble Ln3+−doped calcium fluoride nanocrystals: controlled synthesis and luminescence properties. Mater Lett. 2009;63(21):1794–6.

    Article  Google Scholar 

  • Web of Science. 2015. http://apps.webofknowledge.com/

  • World-Patent. 2011. WO2011116980A1.

    Google Scholar 

  • Wuttke S, Scholz G, Rüdiger S, Kemnitz E. Variation of sol–gel synthesis parameters and their consequence for the surface area and structure of magnesium fluoride. J Mater Chem. 2007;17:4980–8.

    Article  Google Scholar 

  • Wuttke S, Coman SM, Scholz G, Kirmse H, Vimont A, Daturi M, Schröder SLM, Kemnitz E. Novel sol–gel synthesis of acidic MgF2−x(OH)x materials. Chem Eur J. 2008;14:11488–99.

    Article  Google Scholar 

  • Wuttke S, Lehmann A, Scholz G, Feist M, Dimitrov A, Troyanov SI, Kemnitz E. Investigation of the fluorolysis of magnesium methoxide. Dalton Trans. 2009;24:4729–4734.

    Google Scholar 

  • Wuttke S, Vimont A, Lavalley JC, Daturi M, Kemnitz E. Infrared investigation of the acid and basic properties of a sol–gel prepared MgF2. J Phys Chem C. 2010a;114(11):5113–20.

    Article  Google Scholar 

  • Wuttke S, Coman SM, Kröhnert J, Jentoft FC, Kemnitz E. Sol–gel prepared nanoscopic metal fluorides – a new class of tunable acid–base catalysts. Catal Today. 2010b;152(1-4):2–10.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Chemistry Department, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489, Berlin, Germany

    Erhard Kemnitz

Authors
  1. Erhard Kemnitz
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Erhard Kemnitz .

Editor information

Editors and Affiliations

  1. Rutgers University, Piscataway, New Jersey, USA

    Lisa Klein

  2. Madrid, Spain

    Mario Aparicio

  3. City University of New York, New York, USA

    Andrei Jitianu

Rights and permissions

Reprints and permissions

Copyright information

© 2016 Springer International Publishing Switzerland

About this entry

Cite this entry

Kemnitz, E. (2016). Fluorolytic Sol-Gel Processes. In: Klein, L., Aparicio, M., Jitianu, A. (eds) Handbook of Sol-Gel Science and Technology. Springer, Cham. https://doi.org/10.1007/978-3-319-19454-7_114-1

Download citation

  • DOI: https://doi.org/10.1007/978-3-319-19454-7_114-1

  • Received:

  • Accepted:

  • Published:

  • Publisher Name: Springer, Cham

  • Online ISBN: 978-3-319-19454-7

  • eBook Packages: Springer Reference Chemistry and Mat. ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics

Publish with us

Policies and ethics

Search

Navigation