Skip to main content
SpringerLink
Log in

Preparation of fluorinated Cr2O3 hexagonal prism and catalytic performance for the dehydrofluorination of 1,1-difluoroethane to vinyl fluoride

  • Research Paper
  • Published:
Journal of Nanoparticle Research Aims and scope Submit manuscript

Abstract

A Cr2O3 hexagonal prism structure synthesized via the reaction of aqueous CrCl3 solution with NaBH4 solution at room temperature followed by calcination of the precipitate in N2 atmosphere at 500 °C is investigated as an efficient catalyst for dehydrofluorination of 1,1-difluoroethane producing vinyl fluoride. With the assistance of scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy, experimental results revealed that the uniform hexagonal prism has a prism length of 285 ± 43 nm and width of 233 ± 33 nm. It is in the form of loose and net-like aggregation of nano-Cr2O3 with diameter less than 3–5 nm with polycrystalline structure. NH3 temperature programmed desorption and chlorodifluoromethane dismutation experiments confirm the existence of relatively abundant and strong acidic sites. As a catalyst for dehydrofluorination of 1,1-difluoroethane, compared with commercial Cr2O3, much higher activity and stability were observed due to the evolution of CrO x F y species and much higher surface area and mesoporous structure. No significant morphology changes or sintering of the catalyst are observed after 70-h reaction. Compared with the commercial Cr2O3, we suggest that the much smaller size of Cr2O3 crystalline which possesses higher surface energy, lower strength, and more abundant Lewis acidity and the formation of CrO x F y during reaction over hexagonal prism catalyst probably contributes to the activity and stability difference between these two catalysts.

Graphical Abstract

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  • Albonetti S, Forni L, Cuzzato P, Alberani P, Zappoli S, Trifirò F (2007) Aging investigation on catalysts for hydrofluorocarbons synthesis. Appl Catal A 326:48–54

    Article  Google Scholar 

  • Bai G, Dai H, Liu Y, Ji K, Li X, Xie S (2013) Preparation and catalytic performance of cylinder-and cake-like Cr2O3 for toluene combustion. Catal Commun 36:43–47

    Article  Google Scholar 

  • Bai YK, Zheng RT, Gu Q, Wang JJ, Wang BS, Cheng GA, Chen G (2014) One-step synthesis of hollow Cr(OH)3 micro/nano-hexagonal pellets and the catalytic properties of hollow Cr2O3 structures. J Mater Chem A 32:12770–12775

    Article  Google Scholar 

  • Bonniface D, Scott J, Watson M, Fryer J, Scott WS, Winfield J (1999) Halogen exchange reactions for CFC alternatives. The behaviour of fluorine-18 labelled hydrogen fluoride towards prefluorinated chromia containing nickel(II) or zinc(II). Green Chem 1:9–11

    Article  Google Scholar 

  • Brunet S, Requieme B, Colnay E, Barrault J, Blanchard M (1995) Catalytic gas-phase fluorination of 1,1,1-trifluoro-2-chloroethane over chromium (III) oxide: preparation of hydrofluoroalkanes. Appl Catal B 5:305–317

    Article  Google Scholar 

  • Brunet S, Boussand B, Martin D (1997) Properties of Chromium (III) Oxides Involved in the Catalytic Gas Phase Fluorination of CF3CH2Cl. J Catal 171:287–292

    Article  Google Scholar 

  • Brunet S, Boussand B, Rousset A, Andre D (1998) Influence of the morphology and of the composition of chromium oxides on their catalytic activity for the gas phase fluorination of 1,1,1-trifluoro-2-chloro-ethane. Preparation of hydrofluorocarbons. Appl Catal A 168:57–61

    Article  Google Scholar 

  • Cao Z et al (2014) Facile route for synthesis of mesoporous Cr2O3 sheet as anode materials for Li-ion batteries. Electrochim Acta 139:76–81

    Article  Google Scholar 

  • Célérier S, Richard F (2015) Promising heterogeneous catalytic systems based on metal fluorides and oxide hydroxide fluorides: a short review. Catal Commun 67:26–30

    Article  Google Scholar 

  • Chen M et al (2013) SiO2-template synthesis of mesoporous MgF2 highly effective for Cl/F exchange reaction. J Fluorine Chem 150:46–52. doi:10.1016/j.jfluchem.2013.03.003

    Article  Google Scholar 

  • Christoph FJ, Coulston GW, Rao VNM (2002) Treatment of chromium oxide and catalytic manufacture of vinyl fluoride. US Patent 6034289

  • Chung YS, Lee H, Jeong HD, Kim YK, Lee HG, Kim HS, Kim S (1998) Enhanced catalytic activity of air-calcined fluorination catalyst. J Catal 175:220–225

    Article  Google Scholar 

  • Chupas PJ, Ciraolo MF, Hanson JC, Grey CP (2001) In situ X-ray diffraction and solid-state NMR study of the fluorination of γ-Al2O3 with HCF2Cl. J Am Chem Soc 123:1694–1702

    Article  Google Scholar 

  • Ebnesajjad S (2013) 3-Preparation and properties of vinyl fluoride. In: Ebnesajjad S (ed) Polyvinyl fluoride. William Andrew Publishing, New York, pp 25–46. doi:10.1016/B978-1-4557-7885-0.00003-X

    Chapter  Google Scholar 

  • Eltanany G, Rüdiger S, Kemnitz E (2008) Supported high surface AlF3: a very strong solid Lewis acid for catalytic applications. J Mater Chem 19:2268–2275

    Article  Google Scholar 

  • Guisnet M, Magnoux P (2001) Organic chemistry of coke formation. Appl Catal A-Gen 212:83–96. doi:10.1016/S0926-860X(00)00845-0

    Article  Google Scholar 

  • He J et al (2008) Effect of calcination temperature on CrO x –Y2O3 catalysts for fluorination of 2-chloro-1,1,1-trifluoroethane to 1,1,1,2-tetrafluoroethane. J Catal 253:1–10

    Article  Google Scholar 

  • Jia X-Q, H-d Quan, Tamura M, Sekiya A (2012) Synthesis of microporous fluorinated chromia with a sharp pore distribution. RSC Adv 2:6695–6700

    Article  Google Scholar 

  • Jia W, Wu Q, Lang X, Hu C, Zhao G, Li J, Zhu Z (2015) Influence of Lewis acidity on catalytic activity of the porous alumina for dehydrofluorination of 1,1,1,2-tetrafluoroethane to trifluoroethylene. Catal Lett 145:654–661. doi:10.1007/s10562-014-1409-z

    Article  Google Scholar 

  • Jiao K, Zhang B (2005) Growth of porous single-crystal Cr2O3 in a 3-D mesopore system. Chem Commun 45:5618–5620

    Article  Google Scholar 

  • Karamoddin M, Varaminian F (2013) Solubility of R22, R23, R32, R134a, R152a, R125 and R744 refrigerants in water by using equations of state. Int J Refrig 36:1681–1688

    Article  Google Scholar 

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

    Article  Google Scholar 

  • Kemnitz E, Menz D-H (1998) Fluorinated metal oxides and metal fluorides as heterogeneous catalysts. Prog Solid State Chem 26:97–153

    Article  Google Scholar 

  • Kemnitz E, Kohne A, Grohmann I, Lippitz A, Unger W (1996) X-ray photoelectron and x-ray excited auger electron spectroscopic analysis of surface modifications of chromia during heterogeneous catalyzed chlorine/fluorine exchange. J Catal 159:270–279

    Article  Google Scholar 

  • Kemnitz E, Groß U, Rüdiger S, Shekar CS (2003) Amorphous metal fluorides with extraordinary high surface areas. Angew Chem Int Ed 42:4251–4254

    Article  Google Scholar 

  • Kim H, Kim HS, Lee BG, Lee H, Kim S (1995) Effect of magnesium fluoride in chromium–magnesium catalysts on the fluorination reaction of 1,1,1-trifluoro-2-chloroethane. J Chem Soc 23:2383–2384

    Google Scholar 

  • Li G-L, Nishiguchi H, Ishihara T, Moro-oka Y, Takita Y (1998) Catalytic dehydrofluorination of CF3CH3 (HFC143a) into CF2CH2 (HFC1132a). Appl Catal B 16:309–317

    Article  Google Scholar 

  • Loustaunau A, Fayolle-Romelaer R, Celerier S, D’Huysser A, Gengembre L, Brunet S (2010) Catalytic fluorination of various chlorinated hydrocarbons by HF and a chromium based catalyst: effect of the presence of zinc. Catal Lett 138:215–223

    Article  Google Scholar 

  • Lu J-Q et al (2014) Effects of yttrium-doping on the performance of Cr2O3 catalysts for vapor phase fluorination of 1,1,2,3-tetrachloropropene. J Fluor Chem 166:78–83

    Article  Google Scholar 

  • Ma H et al (2012) Highly toluene sensing performance based on monodispersed Cr2O3 porous microspheres. Sensor Actuat B 174:325–331

    Article  Google Scholar 

  • Manzer L, Rao V (1993) Catalytic synthesis of chlorofluorocarbon alternatives. Adv Catal 39:329–350

    Google Scholar 

  • Mao W et al (2014) Selective gas-phase catalytic fluorination of 1,1,2,3-tetrachloropropene to 2-chloro-3, 3, 3-trifluoropropene. Catal Commun 49:73–77

    Article  Google Scholar 

  • Murthy JK, Gross U, Rüdiger S, Ünveren E, Unger W, Kemnitz E (2005) Synthesis and characterization of chromium (III)-doped magnesium fluoride catalysts. Appl Catal A: Gen 282:85–91

    Article  Google Scholar 

  • Pei Z, Zhang Y (2008) A novel method to prepare Cr2O3 nanoparticles. Mater Lett 62:504–506

    Article  Google Scholar 

  • Quan HD, H-e Yang, Tamura M, Sekiya A (2005) Synthesis of a porous chromium fluoride catalyst with a large surface area. J Catal 231:254–257

    Article  Google Scholar 

  • Rai D, Sass BM, Moore DA (1987) Chromium(III) hydrolysis constants and solubility of chromium(III) hydroxide. Inorg Chem 26:345–349

    Article  Google Scholar 

  • Sadakane M, Horiuchi T, Kato N, Takahashi C, Ueda W (2007) Facile preparation of three-dimensionally ordered macroporous alumina, iron oxide, chromium oxide, manganese oxide, and their mixed-metal oxides with high porosity. Chem Mater 19:5779–5785

    Article  Google Scholar 

  • Santulli AC, Feygenson M, Camino FE, Aronson M, Wong SS (2011) Synthesis and characterization of one-dimensional Cr2O3 nanostructures. Chem Mater 23:1000–1008

    Article  Google Scholar 

  • Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (2008) Reporting physisorption data for gas/solid systems. In: Handbook of heterogeneous catalysis. Wiley-VCH Verlag GmbH & Co. KGaA, New York. doi:10.1002/9783527610044.hetcat0065

  • Sinha AK, Suzuki K (2005) Three-dimensional mesoporous chromium oxide: a highly efficient material for the elimination of volatile organic compounds. Angew Chem Int Ed 44:271–273

    Article  Google Scholar 

  • Stewart II, Olesik JW (2000) Investigation of Cr(III) hydrolytic polymerisation products by capillary electrophoresis-inductively coupled plasma-mass spectrometry. J Chromatogr A 872:227–246

    Article  Google Scholar 

  • Teinz K, Wuttke S, Börno F, Eicher J, Kemnitz E (2011) Highly selective metal fluoride catalysts for the dehydrohalogenation of 3-chloro-1,1,1,3-tetrafluorobutane. J Catal 282:175–182

    Article  Google Scholar 

  • Teinz K, Manuel SR, Chen BB, Pigamo A, Doucet N, Kemnitz E (2015) Catalytic formation of 2,3,3,3-tetrafluoropropene from 2-chloro-3,3,3-trifluoropropene at fluorinated chromia: a study of reaction pathways. Appl Catal B-environ 165:200–208

    Article  Google Scholar 

  • Tüysüz H, Weidenthaler C, Grewe T, Salabaş EL, Benitez Romero MJ, Schüth F (2012) A crystal structure analysis and magnetic investigation on highly ordered mesoporous Cr2O3. Inorg Chem 51:11745–11752

    Article  Google Scholar 

  • Wu X, Cong P, Mori S (2002) Adsorption and reactions of HFC-134a gas on the nascent surface of alumina. Appl Surf Sci 201:115–122

    Article  Google Scholar 

  • Xia Y, Dai H, Jiang H, Deng J, He H, Au CT (2009) Mesoporous chromia with ordered three-dimensional structures for the complete oxidation of toluene and ethyl acetate. Environ Sci Technol 43:8355–8360

    Article  Google Scholar 

  • Xu X, Wu J, Yang N, Na H, Li L, Gao J (2015) Cr2O3: a novel supercapacitor electrode material with high capacitive performance. Mater Lett 142:172–175

    Article  Google Scholar 

  • Zhi-Jie L, Rui-Quan L, Ji-De W, Ya-Hong X, Fan Y (2005) Preparation of BaCe0.8Gd0.2O3 by the citrate method and its application in the synthesis of ammonia at atmospheric pressure. J Solid State Electro 9:201–204

    Article  Google Scholar 

Download references

Acknowledgments

The financial supports from the Zhejiang Provincial Natural Science Foundation of China (Grant No. LY12B03007), the Qianjiang Talent Project B in Zhejiang Province (2013R10056), and Special Programs for Research Institutes in Zhejiang (2015F50031) are acknowledged.

Author information

Authors and Affiliations

  1. Institute of Catalysis, Zhejiang University of Technology, Hangzhou, 310014, Zhejiang, People’s Republic of China

    Wenfeng Han, Xiaojuan Li, Haodong Tang, Zhikun Wang, Miao Xi, Ying Li & Huazhang Liu

Authors
  1. Wenfeng Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiaojuan Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Haodong Tang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Zhikun Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Miao Xi
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ying Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Huazhang Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Wenfeng Han.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 3495 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Han, W., Li, X., Tang, H. et al. Preparation of fluorinated Cr2O3 hexagonal prism and catalytic performance for the dehydrofluorination of 1,1-difluoroethane to vinyl fluoride. J Nanopart Res 17, 365 (2015). https://doi.org/10.1007/s11051-015-3170-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11051-015-3170-7

Keywords

Search

Navigation