Montmorillonite supported titanium/antimony catalyst: Preparation, characterization and immobilization

Abstract

Montmorillonite supported titanium (Ti-MMT) or antimony catalyst (Sb-MMT) has been a hot area of research on preparing polyethylene terephthalate/montmorillonite (PET/MMT) nanocomposites by in situ polymerization. So removal of Ti or Sb from Ti-MMT or Sb-MMT is not expected during in situ polymerization. Studies on immobilization of Ti or Sb on Ti-MMT or Sb-MMT are seldom reported. In this work, a series of montmorillonite supported catalysts of titanium (Ti-MMT) or antimony (Sb-MMT) and cointercalated montmorillonite of titanium and antimony (Ti/Sb-MMT) were prepared by (1) the reaction of sodium bentonite suspension with intercalating solution containing titanium tetrachloride and/or antimony chloride, and (2) drying or calcinating the products at different temperature (100, 150, 240, 350 and 450 °C). The physicochemical properties of these MMT supported catalysts were studied by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma optical emission spectrometer (ICPOES), N2 adsorption/desorption isotherms, UV-visible diffuse reflectance spectroscopy(UV-vis) and transmission electron microscopy (TEM). The immobile character of Ti or Sb on MMT supported catalysts was evaluated by a two-step method in deionized water or ethylene glycol. Several results were obtained, i e, (a) during the preparation, with an increase in drying or calcinating temperature, the amount of titanium and/or antimony species remained on these MMT supported catalysts decreased, (b) the experiments about immobile character of Ti or/and Sb showed that with an increase in drying or calcinating temperature, the immobilization of Ti and/or Sb species remained on these MMT supported catalysts increased gradually, (c) Ti-MMT calcinated at 450 °C had the biggest pore volume, which means Ti-MMT had the best adsorption application prospect.

Keywords

montmorillonite / titanium / antimony / intercalation / immobilization

References

[1] Chen J Y, Li G Y, He Z G, . Adsorption and Degradation of Model Volatile Organic Compounds by a Combined Titania-montmorillonitesilica Photocatalyst[J]. Journal of Hazardous Materials, 2011, 190: 416-423.

[2] Is F, Wang S B, Narsito, . Composites of TiO₂-aluminum Pillared Montmorillonite: Synthesis, Characterization and Photocatalytic Degradation Of Methylene Blue[J]. Applied Clay Science, 2010, 50: 588-593.

[3] Yuan L L, Huang D D, Guo W N, . TiO₂/Montmorillonite Nanocomposite for Removal of Organic Pollutant[J]. Applied Clay Science, 2011, 53: 272-278.

[4] Zhang Y, Chen A P, Li C Z, . Laminar Mesoporous Structure of Modified Montmorillonite Clays and Its Formation Mechanism[J]. J. Wuhan Univ. Technol. -Mater. Sci. Ed., 2012, 27: 321-327.

[5] Wang Y M, Gao J P, Ma Y Q, . Study on Mechanical Properties, Thermal Stability and Crystallization Behaviour of PET/MMT Nanocomposites[J]. Composites: Part B, 2006, 37: 399-407.

[6] Ou C F, Ho M T, Lin J R The Nucleating Effect of Montmorillonite on Crystallization of PET/Montmorillonite Nanocomposite[J]. J. Wuhan Univ. Technol. -Mater. Sci. Ed., 2003, 10: 127-132.

[7] Elinor L B, Syozo M, Taku K, . Structural Development and Mechanical Properties of Polyethylene Naphthalate/Polyethylene Terephthalate Blends during Uniaxial Drawing[J]. Polymer, 2001, 42: 7 299-7 305.

[8] Won J C, Hee J K, Kwan H Y, . Preparation and Barrier Property of Poly(ethylene terephthalate)/Clay Nanocomposite Using Clay-Supported Catalyst[J]. Journal of Applied Polymer Science, 2006, 100: 4 875-4 879.

[9] Krzysztof K, Werner S, Gabriela B P, . Exfoliation of Montmorillonite in Protein Solutions[J]. Journal of Colloid and Interface Science, 2012, 374: 135-140.

[10] Ke Y C, Yang Z B, Zhu C F, . Investigation of Properties, Nanostructure, and Distribution in Controlled Polyester Polymerization with Layered Silicate[J]. Journal of Applied Polymer Science, 2002, 85: 2 677-2 691.

[11] Antoniadis G, Paraskevopoulos K M, Vassiliou A A, . Nonisothermal Melt-crystallization Kinetics for In Situ Prepared Poly(ethylene terephthalate)/Monmorilonite (PET/OMMT)[J]. Thermochimica Acta, 2011, 521: 161-169.

[12] Kim S H, Park S H, Kim S C Novel Clay Treatment and Preparation of Poly(ethylene terephthalate)/Clay Nanocomposite by In-situ Polymerization[J]. J. Wuhan Univ. Technol. -Mater. Sci. Ed., 2005, 53: 285-292.

[13] Tsai T Y, Li C H, Chang C H, . Preparation of Exfoliated Polyester/Clay Nanocomposites[J]. Adv. Mater., 2005, 17: 1 769-1 773.

[14] Fu X, Qutubuddin S Polymer-clay Nanocomposites: Exfoliation of Organophilic Montmorillonite Nanolayers in Polystyrene[J]. Polymer, 2001, 42: 807-813.

[15] Rohan L, Elizabeth A L, Saleh A J Improved Method for Dispersing Clay in a Monomer or Bis(2-hydroxyl ethyl terephthalate) Before In Situ Polymerization of Poly(ethylene terephthalate)/Montmorillonite Nanocomposites[J]. Journal of Applied Polymer Science, 2012, 125: 369-381.

[16] Wen B, Xu X F, Gao X W, . Highly Exfoliated Poly(Ethylene Terephthalate)/Clay Nanocomposites via Melt Compounding: Effects of Silane Grafting[J]. Polymer-Plastics Technology and Engineering, 2011, 50: 362-371.

[17] Salah A H, Fatma Z Y, Hamdi A H, . Various Characteristics and Catalytic Performance of Iron (II) Phthalocyanine Immobilized onto Titania- and Vanadia-pillared Bentonite Clay in In Situ Polymerization of Methyl Methacrylate an Attempt to Synthesize Novel Polymer/Iron Phthalocyanine/Pillared Clay Nanocomposites[J]. Journal of Molecular Catalysis A: Chemical, 2010, 332: 93-105.

[18] Zhao Z L, Wang X Q, Zhao C, . Adsorption and Desorption of Antimony Acetate on Sodium Montmorillonite[J]. Journal of Colloid and Interface Science, 2010, 345: 154-159.

[19] Zhao C, Wang X Q, Du S Y Influence of Drying and Calcination on Remaining Amount and Immobile Character of Titanium on Titaniumpillared Montmorillonite[J]. Chin. J. Chem., 2012, 30: 1 017-1 021.

[20] Valverde J L, SJ L, d P, Dorado F, . Influence of the Synthesis Conditions on the Preparation of Titanium-pillared Clays Using Hydrolyzed Titanium Ethoxide as the Pillaring Agent[J]. Microporous and Mesoporous Materials, 2002, 54: 155-165.

[21] Zhang W Z, Froba M, Wang J L, . Mesoporous Titanosilicate Molecular Sieves Prepared at Ambient Temperature by Electrostatic (S⁺I⁻, S⁺X⁻I⁺) and Neutral (S°I°) Assembly Pathways: A Comparison of Physical Properties and Catalytic Activity for Peroxide Oxidations[J]. J. Am. Chem. Soc., 1996, 118: 9 164-9 171.

[22] Wang X Q, Wang Y Q, Zhao Z L, . Preparation and Characterization of Exfoliated Poly(ethyleneterephthalate)/Montmorillonite Nanocomposites Using Modified MMTs with Variable Content of Antimony Acetate[J]. Chin. J. Chem., 2011, 29: 2 421-2 427.