Rapid fabrication of mesoporous titania films with controlled macroporosity to improve photocatalytic property.

Hierarchically porous titania films were fabricated by dual templating using a triblock copolymer such as Pluronic F127 and polystyrene (PS) beads, affording mesoporous films with controlled macroporosity. The presence of the triblock copolymer in the precursor solutions suppressed a regular accumulation of spherical PS beads, and PS-derived macropores could be dispersed over the whole mesoporous titania film through rapid fabrication by spin-coating. Some of the macropores were clustered, but the presence of the large spaces was important for keeping the mesostructure after calcination. Photodegradation of methylene blue (MB) was investigated by using the photoactive anatase films. The photodegradation of MB over the porous anatase films was accelerated by effective diffusion of MB molecules in the PS-derived macropores, but it was important for improving photocatalytic performance to regulate the balance between the effectiveness of the diffusion in the macropores and the decrease of the surface area from the embedded macropores, as well as the reduction in the transparency of the porous films.

[1]  Kazumi Kato,et al.  Triblock copolymer templated semi-crystalline mesoporous titania films containing emulsion-induced macropores , 2009 .

[2]  T. Ohji,et al.  Adsorption Property of Dye Molecule over Semi-Crystalline Mesoporous Titania Films , 2008 .

[3]  C. Sanchez,et al.  Pyrolysis, crystallization, and sintering of mesostructured titania thin films assessed by in situ thermal ellipsometry. , 2008, Journal of the American Chemical Society.

[4]  U. Lee,et al.  Mesoporous titania thin film with highly ordered and fully accessible vertical pores and crystalline walls. , 2008, Chemistry, an Asian journal.

[5]  Jean-François Bardeau,et al.  Visible‐Light Photocatalysis in Titania‐Based Mesoporous Thin Films , 2008 .

[6]  D. Weng,et al.  Achievement of thick mesoporous TiO2 crystalline films by one-step dip-coating approach , 2008 .

[7]  L. Kavan,et al.  Multilayer Films from Templated TiO2 and Structural Changes during their Thermal Treatment , 2008 .

[8]  Haoshen Zhou,et al.  Supercritical fluid processing of mesoporous crystalline TiO2 thin films for highly efficient dye-sensitized solar cells , 2007 .

[9]  Jiaguo Yu,et al.  Template‐Free Fabrication and Enhanced Photocatalytic Activity of Hierarchical Macro‐/Mesoporous Titania , 2007 .

[10]  Ying Wan,et al.  On the controllable soft-templating approach to mesoporous silicates. , 2007, Chemical reviews.

[11]  F. Iskandar,et al.  Enhanced Photocatalytic Performance of Brookite TiO2 Macroporous Particles Prepared by Spray Drying with Colloidal Templating , 2007 .

[12]  M. Srinivasan,et al.  Degradation of methylene blue by three-dimensionally ordered macroporous titania. , 2007, Environmental science & technology.

[13]  W. Ho,et al.  Photocatalytic activity and photo-induced hydrophilicity of mesoporous TiO2 thin films coated on aluminum substrate , 2007 .

[14]  Thierry Gacoin,et al.  Transparent Mesoporous Nanocomposite Films for Self‐Cleaning Applications , 2007 .

[15]  T. Brezesinski,et al.  Highly Organized Mesoporous TiO2 Films with Controlled Crystallinity: A Li‐Insertion Study , 2007 .

[16]  Galo J. A. A. Soler-Illia,et al.  Optimised photocatalytic activity of grid-like mesoporous TiO2 films: effect of crystallinity, pore size distribution, and pore accessibility , 2006 .

[17]  Philippe Belleville,et al.  All‐Solid‐State Dye‐Sensitized Nanoporous TiO2 Hybrid Solar Cells with High Energy‐Conversion Efficiency , 2006 .

[18]  Changhua Wang,et al.  A novel preparation of three-dimensionally ordered macroporous M/Ti (M=Zr or Ta) mixed oxide nanoparticles with enhanced photocatalytic activity. , 2006, Journal of colloid and interface science.

[19]  Zhong‐Yong Yuan,et al.  New Pd/hierarchical macro-mesoporous ZrO2, TiO2 and ZrO2-TiO2 catalysts for VOCs total oxidation , 2006 .

[20]  T. Kunitake,et al.  Efficient fabrication and enhanced photocatalytic activities of 3D-ordered films of titania hollow spheres. , 2006, The journal of physical chemistry. B.

[21]  John Wang,et al.  Substrate-Assisted Crystallization and Photocatalytic Properties of Mesoporous TiO2 Thin Films , 2006 .

[22]  T. Ohsuna,et al.  Formation of highly ordered mesoporous titania films consisting of crystalline nanopillars with inverse mesospace by structural transformation. , 2006, Journal of the American Chemical Society.

[23]  Galo J. A. A. Soler-Illia,et al.  Processing of macroporous titania thin films : From multiscale functional porosity to nanocrystalline macroporous TiO2 , 2006 .

[24]  M. Maggini,et al.  Mesostructured self-assembled titania films for photovoltaic applications , 2006 .

[25]  P Cool,et al.  Preparation and characterization of vanadium oxide deposited on thermally stable mesoporous titania. , 2006, The journal of physical chemistry. B.

[26]  Ladislav Kavan,et al.  Organized mesoporous TiO2 films exhibiting greatly enhanced performance in dye-sensitized solar cells. , 2005, Nano letters.

[27]  G. Stucky,et al.  3-D molecular assembly of function in titania-based composite material systems. , 2005, Accounts of chemical research.

[28]  Xianzhi Fu,et al.  Photocatalytic activity of a hierarchically macro/mesoporous titania. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[29]  B. Su,et al.  Facile and Generalized Preparation of Hierarchically Mesoporous−Macroporous Binary Metal Oxide Materials , 2004 .

[30]  Ryan T. Turgeon,et al.  Multistep, low-temperature pseudomorphic transformations of nanostructured silica to titania via a titanium oxyfluoride intermediate , 2004 .

[31]  Yiying Wu,et al.  Synthesis and photocatalytic properties of highly crystalline and ordered mesoporous TiO2 thin films. , 2004, Chemical communications.

[32]  M. Antonietti,et al.  Highly crystalline cubic mesoporous TiO₂ with 10-nm pore diameter made with a new block copolymer template , 2004 .

[33]  Galo J. A. A. Soler-Illia,et al.  Fundamentals of Mesostructuring Through Evaporation‐Induced Self‐Assembly , 2004 .

[34]  A. Collins,et al.  Spontaneous template-free assembly of ordered macroporous titania. , 2004, Chemical communications.

[35]  Galo J. A. A. Soler-Illia,et al.  Highly porous TiO2 anatase optical thin films with cubic mesostructure stabilized at 700 °C , 2003 .

[36]  Michael D. McGehee,et al.  Photovoltaic cells made from conjugated polymers infiltrated into mesoporous titania , 2003 .

[37]  R. Caruso,et al.  Inorganic Macroporous Films from Preformed Nanoparticles and Membrane Templates: Synthesis and Investigation of Photocatalytic and Photoelectrochemical Properties , 2003 .

[38]  B. Su,et al.  Hierarchically Mesostructured Titania Materials with an Unusual Interior Macroporous Structure , 2003 .

[39]  Eduardo Enciso,et al.  Micro/nano-structural properties of imprinted macroporous titania and zirconia , 2003 .

[40]  David Grosso,et al.  Controlled formation of highly organized mesoporous titania thin films: from mesostructured hybrids to mesoporous nanoanatase TiO2. , 2003, Journal of the American Chemical Society.

[41]  A. Cheetham,et al.  Hierarchically mesoporous/macroporous metal oxides templated from polyethylene oxide surfactant assemblies. , 2003, Angewandte Chemie.

[42]  D. Zhao,et al.  Recent advances in the synthesis of non-siliceous mesoporous materials , 2003 .

[43]  D. Zhao,et al.  Self-adjusted synthesis of ordered stable mesoporous minerals by acid–base pairs , 2003, Nature materials.

[44]  Galo J. A. A. Soler-Illia,et al.  Block copolymer-templated mesoporous oxides , 2003 .

[45]  D. K. Yi,et al.  Novel Approach to the Fabrication of Macroporous Polymers and Their Use as a Template for Crystalline Titania Nanorings , 2003 .

[46]  Galo J. A. A. Soler-Illia,et al.  Nanocrystallised titania and zirconia mesoporous thin films exhibiting enhanced thermal stability , 2003 .

[47]  R. Brüning,et al.  Preparation of Large‐Area 3D Ordered Macroporous Titania Films by Silica Colloidal Crystal Templating , 2003 .

[48]  Dong Yang,et al.  Eggshell Membrane Templating of Hierarchically Ordered Macroporous Networks Composed of TiO2 Tubes , 2002 .

[49]  Bénédicte Lebeau,et al.  Chemical strategies to design textured materials: from microporous and mesoporous oxides to nanonetworks and hierarchical structures. , 2002, Chemical reviews.

[50]  E. Enciso,et al.  Macroporous silica and titania obtained using poly[styrene-co-(2-hydroxyethyl methacrylate)] as template , 2002 .

[51]  D. Zhao,et al.  Fast preparation of highly ordered nonsiliceous mesoporous materials via mixed inorganic precursors. , 2002, Chemical communications.

[52]  R. Hayward,et al.  General Predictive Syntheses of Cubic, Hexagonal, and Lamellar Silica and Titania Mesostructured Thin Films§ , 2002 .

[53]  D. Kuang,et al.  Fabrication of ordered macroporous rutile titania at low temperature , 2002 .

[54]  Seung‐Man Yang,et al.  Ordered Macroporous Particles by Colloidal Templating , 2001 .

[55]  Galo J. A. A. Soler-Illia,et al.  Highly Organized Mesoporous Titania Thin Films Showing Mono-Oriented 2D Hexagonal Channels , 2001 .

[56]  M. Bousmina,et al.  Preparation of macrostructured metal oxides by sedimentation–aggregation , 2001 .

[57]  A. Stein,et al.  Gems of Chemistry and Physics: Macroporous Metal Oxides with 3D Order , 2001 .

[58]  D. Pine,et al.  Photonic Crystals from Emulsion Templates , 2001 .

[59]  V. Colvin,et al.  Thin Films of Macroporous Metal Oxides , 2001 .

[60]  F. Caruso,et al.  Synthesis of macroporous titania and inorganic composite materials from coated colloidal spheres - A novel route to tune pore morphology. , 2001 .

[61]  Bradley F. Chmelka,et al.  Block Copolymer Templating Syntheses of Mesoporous Metal Oxides with Large Ordering Lengths and Semicrystalline Framework , 1999 .

[62]  Andreas Stein,et al.  Synthesis of highly ordered, three-dimensional, macroporous structures of amorphous or crystalline inorganic oxides, phosphates, and hybrid composites , 1999 .

[63]  Bradley F. Chmelka,et al.  Generalized syntheses of large-pore mesoporous metal oxides with semicrystalline frameworks , 1998, Nature.

[64]  Vos,et al.  Preparation of photonic crystals made of air spheres in titania , 1998, Science.

[65]  A. Stein,et al.  Synthesis of macroporous minerals with highly ordered three-dimensional arrays of spheroidal voids , 1998, Science.

[66]  D. Pine,et al.  Uniform Macroporous Ceramics and Plastics by Emulsion Templating , 1998 .

[67]  A. Imhof,et al.  Ordered macroporous materials by emulsion templating , 1997, Nature.

[68]  A. Nozik,et al.  Moessbauer study of the kinetics of iron(3+) photoreduction on titanium dioxide semiconductor powders , 1985 .

[69]  Sung Yeun Choi,et al.  Pore architecture affects photocatalytic activity of periodic mesoporous nanocrystalline anatase thin films , 2007 .

[70]  F. Caruso,et al.  Fabrication of heterogeneous macroporous materials based on a sequential electrostatic deposition process , 2001 .

[71]  K. C. Lee,et al.  Nanoparticle routes to mesoporous titania thin films. , 2001, Chemical communications.