Photocatalytic and adsorption properties of TiO2-pillared montmorillonite obtained by hydrothermally activated intercalation of titanium polyhydroxo complexes

We report on a new approach for the synthesis of TiO2-pillared montmorillonite, where the pillars exhibit a high degree of crystallinity (nanocrystals) representing a mixture of anatase and rutile phases. The structures exhibit improved adsorption and photocatalytic activity as a result of hydrothermally activated intercalation of titanium polyhydroxo complexes (i.e., TiCl4 hydrolysis products) in a solution with a concentration close to the sol formation limit. The materials, produced at various annealing temperatures from the intercalated samples, were characterized by infrared spectroscopy, differential scanning calorimetry (DSC)/thermogravimetric analysis (TGA), X-ray diffraction, dynamic light scattering (DLS) measurements, and liquefied nitrogen adsorption/desorption. The photocatalytic activity of the TiO2-pillared materials was studied using the degradation of anionic (methyl orange, MO) and cationic (rhodamine B, RhB) dyes in water under UV irradiation. The combined effect of adsorption and photocatalysis resulted in removal of 100% MO and 97.5% RhB (with an initial concentration of 40 mg/L and a photocatalyst-sorbent concentration of 1 g/L) in about 100 minutes. The produced TiO2-pillared montmorillonite showed increased photocatalytic activity as compared to the commercially available photocatalyst Degussa P25.

[1]  B. Szczepanik.  Photocatalytic degradation of organic contaminants over clay-TiO2 nanocomposites: A review , 2017 .

[2]  A. Vinogradov,et al.  Photocatalytic Activity of Biomorphic TiO2 Fibers Obtained by Ultrasound-Assisted Impregnation of Cellulose with Titanium Polyhydroxocomplexes , 2017 .

[3]  Chenze Qi,et al.  Study on the preparation and characterization of a titanium-pillared clay-supported CrCe catalyst and its application to the degradation of a low concentration of chlorobenzene , 2015 .

[4]  R. Socha,et al.  (Ti,Zr)-pillared montmorillonite - A new quality with respect to Ti- and Zr-pillared clays , 2015 .

[5]  C. Bianchi,et al.  Photoactive TiO2–montmorillonite composite for degradation of organic dyes in water , 2014 .

[6]  J. Shapter,et al.  Influence of dimensions, inter-distance and crystallinity of titania nanotubes (TNTs) on their photocatalytic activity , 2014 .

[7]  F. Figueras,et al.  Photocatalytic degradation of anionic and cationic dyes over TiO2 P25, and Ti-pillared clays and Ag-doped Ti-pillared clays , 2014 .

[8]  T. V. Kon’kova,et al.  Adsorption properties of pillared clays , 2014, Protection of Metals and Physical Chemistry of Surfaces.

[9]  M. S. Giri Nandagopal,et al.  Relevance of isotherm models in biosorption of pollutants by agricultural byproducts , 2014 .

[10]  M. Petkovska.  Discrimination between adsorption isotherm models based on nonlinear frequency response results , 2014, Adsorption.

[11]  Daimei Chen,et al.  Synthesis and characterization of TiO2 pillared montmorillonites: application for methylene blue degradation. , 2013, Journal of colloid and interface science.

[12]  Daimei Chen,et al.  Synthesis and photocatalytic performances of the TiO2 pillared montmorillonite. , 2012, Journal of hazardous materials.

[13]  T. Aaltonen,et al.  Glass-encapsulated light harvesters: more efficient dye-sensitized solar cells by deposition of self-aligned, conformal, and self-limited silica layers. , 2012, Journal of the American Chemical Society.

[14]  M. Baraton.  Nano-TiO2 for Solar Cells and Photocatalytic Water Splitting:Scientific and Technological Challenges for Commercialization , 2011 .

[15]  M. Gasparon,et al.  Infrared Spectroscopy of Titania Sol-Gel Coatings on 316L Stainless Steel , 2011 .

[16]  L. Duclaux,et al.  Preparation of TiO2-pillared montmorillonite as photocatalyst Part II: Photocatalytic degradation of a textile azo dye , 2009 .

[17]  L. Duclaux,et al.  Preparation of TiO2-pillared montmorillonite as photocatalyst Part I. Microwave calcination, characterisation, and adsorption of a textile azo dye , 2009 .

[18]  Yu. O. Nikitin,et al.  Structure features of modified thermally extended graphite , 2008 .

[19]  G. Petasyuk,et al.  Specific surface area determination methods, devices, and results for diamond powders , 2008 .

[20]  J. Zhou,et al.  Low-temperature synthesis and photocatalytic activity of TiO2 pillared montmorillonite. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[21]  Zhengwen Yang,et al.  Enhanced photocatalytic activity of microwave treated TiO2 pillared montmorillonite , 2006 .

[22]  Jinlong Zhang,et al.  Preparation of controllable crystalline titania and study on the photocatalytic properties. , 2005, The journal of physical chemistry. B.

[23]  S. Azizian.  Kinetic models of sorption: a theoretical analysis. , 2004, Journal of colloid and interface science.

[24]  H. Yoshida,et al.  Highly hydrophobic TiO2 pillared clay for photocatalytic degradation of organic compounds in water , 2004 .

[25]  D. Bousfield,et al.  Formation of a thin TiO2 layer on the surfaces of silica and kaolin pigments through atomic layer deposition , 2003 .

[26]  J. Domínguez,et al.  Catalytic hydrotreating of heavy vacuum gas oil on Al- and Ti-pillared clays prepared by conventional and microwave irradiation methods , 2003 .

[27]  K. Otake,et al.  TiO2-montmorillonite composites via supercritical intercalation. , 2002, Chemical communications.

[28]  Shi Erwei,et al.  Formation of zirconia polymorphs under hydrothermal conditions , 2002 .

[29]  T. Kodama,et al.  Synthesis and Photocatalytic Activity of Titania Pillared Clays , 2001 .

[30]  Y. Ho,et al.  Pseudo-second order model for sorption processes , 1999 .

[31]  N. Xu,et al.  Effects of Particle Size of TiO2 on Photocatalytic Degradation of Methylene Blue in Aqueous Suspensions , 1999 .

[32]  Gordon McKay,et al.  The kinetics of sorption of basic dyes from aqueous solution by sphagnum moss peat , 1998 .

[33]  F. Castellano,et al.  Spectroscopic and excited-state properties of titanium dioxide gels , 1994 .

[34]  P. Grange,et al.  Synthesis and Characterization of Titanium Pillared Clays - Influence of the Temperature of Preparation , 1991 .

[35]  C. Pesquera,et al.  Differences Between One Aluminic Palygorskite and Another Magnesic by Infrared Spectroscopy , 1989 .

[36]  J. Sterte.  Synthesis and Properties of Titanium Oxide Cross-Linked Montmorillonite , 1986 .

[37]  A. Huitson,et al.  A general treatment and classification of the solute adsorption isotherm. I. Theoretical , 1974 .

[38]  H. Myers,et al.  Quantitative Analysis of Anatase-Rutile Mixtures with an X-Ray Diffractometer , 1957 .

[39]  Hexing Li,et al.  Nanostructured Photocatalysts: Advanced Functional Materials , 2016 .

[40]  E. Galán,et al.  Structure and Mineralogy of Clay Minerals , 2013 .

[41]  A. Gil,et al.  Pillared Clays and Clay Minerals , 2013 .

[42]  V. Vinogradov,et al.  Surfactant-Assisted Sol-Gel Synthesis of TiO 2 with Uniform Particle Size Distribution , 2011 .

[43]  Huaiyong Zhu,et al.  Novel strategies towards mesoporous titania and titania-silicate composites , 2004 .

[44]  R. Schoonheydt,et al.  Chapter 7 Clays: From two to three dimensions , 2001 .

[45]  Zhu,et al.  Photocatalytic Properties of Titania Pillared Clays by Different Drying Methods. , 1999, Journal of colloid and interface science.

[46]  H. Yoshida,et al.  Crystallization of hydrothermally treated TiO2 pillars in pillared montmorillonite for improvement of the photocatalytic activity , 1999 .

[47]  S. Allen,et al.  Intraparticle diffusion of a basic dye during adsorption onto sphagnum peat. , 1989, Environmental pollution.

[48]  Bernard Delmon,et al.  Studies in Surface Science and Catalysis , 1988 .

[49]  R. Howie,et al.  Crystal growth , 1982, Nature.

[50]  H. Einaga.  Hydrolysis of titanium(IV) in aqueous (Na,H)Cl solution , 1979 .

[51]  S. Ross.  The Infrared Spectra of Minerals , 1974 .

[52]  S. Lagergren,et al.  Zur Theorie der sogenannten Adsorption gelöster Stoffe , 1898 .

[53]  R. Pierotti,et al.  International Union of Pure and Applied Chemistry Physical Chemistry Division Commission on Colloid and Surface Chemistry including Catalysis* Reporting Physisorption Data for Gas/solid Systems with Special Reference to the Determination of Surface Area and Porosity Reporting Physisorption Data for , 2022 .