Macro-/mesoporous titania thin films: analysing the effect of pore architecture on photocatalytic activity using high-throughput screening

Hierarchically porous, anatase titania thin films were fabricated by a one-pot, soft-templating technique combined with a phase separation route. The pore structure was readily tuned by adjusting the concentration of the polymeric components added during the sol–gel synthesis. Poly(vinylpyrrolidone) (PVP) altered the three dimensional pore structure, generating macroporous networks within the films. The effect of the morphological modifications on the photocatalytic activity of titania was investigated by the photodegradation of methylene blue using high-throughput screening, with the macroporous arrangement of the films significantly influencing photocatalytic activity. The highest photocatalytic activity under UV irradiation normalised by the accessible surface area was obtained by porous titania thin films prepared using 1:1:0 poly(ethylene glycol):PVP:Pluronic® F127. The addition of F127 did increase the overall photocatalytic activity, but lowered the activity per unit area because of obstructed light penetration. These results provide insight into the effect of regulating the pore morphology of titania thin films to further enhance their potential as immobilised photocatalytic reactors.

[1]  R. Caruso,et al.  High-Throughput Synthesis and Screening of Titania-Based Photocatalysts. , 2015, ACS combinatorial science.

[2]  G. Mul,et al.  High throughput analysis of photocatalytic water purification. , 2014, Analytical chemistry.

[3]  T. Do,et al.  Three-dimensional ordered assembly of thin-shell Au/TiO2 hollow nanospheres for enhanced visible-light-driven photocatalysis. , 2014, Angewandte Chemie.

[4]  K. Nakanishi,et al.  Preparation and characterization of macroporous TiO2–SrTiO3 heterostructured monolithic photocatalyst , 2014 .

[5]  Heqing Yang,et al.  Synthesis and characterization of hierarchical titania-silica monolith , 2013 .

[6]  A. Fujishima,et al.  Preparation and photocatalytic activity of robust titania monoliths for water remediation. , 2013, ACS applied materials & interfaces.

[7]  Jie Zhang,et al.  Quantitative Detection of OH Radicals for Investigating the Reaction Mechanism of Various Visible-Light TiO2 Photocatalysts in Aqueous Suspension , 2013 .

[8]  Galo J. A. A. Soler-Illia,et al.  Synthesis and photocatalytic activity of titania monoliths prepared with controlled macro- and mesopore structure. , 2012, ACS applied materials & interfaces.

[9]  Krishna Rajan,et al.  Combinatorial and high-throughput screening of materials libraries: review of state of the art. , 2011, ACS combinatorial science.

[10]  Qingliu Wu,et al.  Hierarchically porous titania thin film prepared by controlled phase separation and surfactant templating. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[11]  Qingliu Wu,et al.  Tuning the Mesopore Size of Titania Thin Films Using a Polymeric Swelling Agent , 2011 .

[12]  Jin Zhai,et al.  Hierarchically ordered macro-mesoporous TiO₂-graphene composite films: improved mass transfer, reduced charge recombination, and their enhanced photocatalytic activities. , 2011, ACS nano.

[13]  X. M. Zhang,et al.  Optofluidic planar reactors for photocatalytic water treatment using solar energy. , 2010, Biomicrofluidics.

[14]  Hong Huang,et al.  Effect of polyethylene glycol on hydrophilic TiO2 films: Porosity-driven superhydrophilicity , 2010 .

[15]  Galo J. A. A. Soler-Illia,et al.  One-Pot Synthesis of Hierarchically Structured Ceramic Monoliths with Adjustable Porosity , 2010 .

[16]  J. Janek,et al.  Mesoporous TiO(2): comparison of classical sol-gel and nanoparticle based photoelectrodes for the water splitting reaction. , 2010, ACS nano.

[17]  C. Xie,et al.  Synthesis of TiO(2)/WO(3)/MnO(2) composites and high-throughput screening for their photoelectrical properties. , 2010, Journal of combinatorial chemistry.

[18]  M. A. Meneses Nava,et al.  The influence of polyvinylpyrrolidone on thick and optical properties of BaTiO3:Er3+ thin films prepared by sol–gel method , 2010 .

[19]  I. Parkin,et al.  Simple method for the rapid simultaneous screening of photocatalytic activity over multiple positions of self-cleaning films. , 2009, Physical chemistry chemical physics : PCCP.

[20]  N. Miyamoto,et al.  Rapid fabrication of mesoporous titania films with controlled macroporosity to improve photocatalytic property. , 2009, Chemistry, an Asian journal.

[21]  Cara M. Doherty,et al.  Colloidal Crystal Templating to Produce Hierarchically Porous LiFePO4 Electrode Materials for High Power Lithium Ion Batteries , 2009 .

[22]  Galo J. A. A. Soler-Illia,et al.  One-Pot Route to Produce Hierarchically Porous Titania Thin Films by Controlled Self-Assembly, Swelling, and Phase Separation , 2009 .

[23]  G. Ozin,et al.  Heterogeneous photocatalysis with inverse titania opals: probing structural and photonic effects , 2009 .

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

[25]  F. Di Fonzo,et al.  Hierarchically organized nanostructured TiO2 for photocatalysis applications , 2008, Nanotechnology.

[26]  J. Wu,et al.  Photoreduction of CO2 to fuels under sunlight using optical-fiber reactor , 2008 .

[27]  A. Mills,et al.  A rapid method of assessing the photocatalytic activity of thin TiO2 films using an ink based on the redox dye 2,6-dichloroindophenol , 2008 .

[28]  Jiaguo Yu,et al.  A One-Pot Approach to Hierarchically Nanoporous Titania Hollow Microspheres with High Photocatalytic Activity , 2008 .

[29]  G. Camera-Roda,et al.  Optimization of the thickness of a photocatalytic film on the basis of the effectiveness factor , 2007 .

[30]  Jiaguo Yu,et al.  Hydrothermal Preparation and Photocatalytic Activity of Hierarchically Sponge-like Macro-/Mesoporous Titania , 2007 .

[31]  K. Fujita,et al.  Monolithic TiO2 with controlled multiscale porosity via a template-free sol-gel process accompanied by phase separation , 2006 .

[32]  Geoffrey A. Ozin,et al.  Amplified Photochemistry with Slow Photons , 2006 .

[33]  T. Yin,et al.  Preparation of nanocrystalline TiO2 porous films from terpineol-ethanol-PEG system , 2006 .

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

[35]  R. Caruso,et al.  Agarose template for the fabrication of macroporous metal oxide structures. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[36]  J. Pan,et al.  Selective control of cubic and hexagonal mesophases for titania and silica thin films with spin-coating , 2005 .

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

[38]  Zhengguo Jin,et al.  Synthesis of TiO2 porous thin films by polyethylene glycol templating and chemistry of the process , 2005 .

[39]  Kazuyuki Hirao,et al.  Preparation of Macroporous Titania Films by a Sol‐Gel Dip‐Coating Method from the System Containing Poly(ethylene glycol) , 2005 .

[40]  Zhengguo Jin,et al.  Preparation and Formation Mechanism of Porous TiO2 Films Using PEG and Alcohol Solvent as Double-Templates , 2004 .

[41]  M. Uehara,et al.  Modified micro-space using self-organized nanoparticles for reduction of methylene blue. , 2003, Chemical communications.

[42]  M. Stylidi.  Pathways of solar light-induced photocatalytic degradation of azo dyes in aqueous TiO2 suspensions , 2003 .

[43]  M. Moo-young,et al.  Preliminary analysis of a tellerette packed-bed photocatalytic reactor , 2002 .

[44]  A. Nakayama,et al.  Development of high throughput evaluation for photocatalyst thin-film , 2002 .

[45]  Y. Qian,et al.  Synthesis of closed PbS nanowires with regular geometric morphologies , 2002 .

[46]  W. Maier,et al.  Combinatorial Discovery of New Photocatalysts for Water Purification with Visible Light. , 2001, Angewandte Chemie.

[47]  J. Herrmann,et al.  Photocatalytic degradation pathway of methylene blue in water , 2001 .

[48]  Jiaguo Yu,et al.  Preparation and characterization of super-hydrophilic porous TiO2 coating films , 2001 .

[49]  K. Nakanishi,et al.  Macroporous morphology of titania films prepared by sol-gel dip-coating method from a system containing poly(ethylene glycol) and poly(vinylpyrrolidone) , 2001 .

[50]  Jiaguo Yu,et al.  Effect of surface structure on photocatalytic activity of TiO2 thin films prepared by sol-gel method , 2000 .

[51]  R. Caruso,et al.  Cellulose acetate templates for porous inorganic network fabrication. , 2000 .

[52]  T. Yao,et al.  Macroporous Morphology of the Titania Films Prepared by a Sol-Gel Dip-Coating Method from the System Containing Poly(ethylene glycol): Effects of Molecular Weight and Dipping Temperature , 2000 .

[53]  H. Kozuka,et al.  Crack-Free, Thick Ceramic Coating Films via Non-Repetitive Dip-Coating Using Polyvinylpyrrolidone as Stress-Relaxing Agent , 2000 .

[54]  and Yong Soon Park,et al.  Correlation between Surface Morphology and Hydrophilic/Hydrophobic Conversion of MOCVD−TiO2 Films , 2000 .

[55]  T. Yao,et al.  Macroporous Morphology of the Titania Films Prepared by a Sol-Gel Dip-Coating Method from the System Containing Poly(ethylene glycol). IV. General Principle of Morphology Formation and Effect of Heat Treatment , 2000 .

[56]  Haike Yan,et al.  Adsorption of Methylene Blue on Montmorillonite , 1999 .

[57]  Stephen Mann,et al.  Bacterial templating of ordered macrostructures in silica and silica-surfactant mesophases , 1997, Nature.

[58]  A. Cassano,et al.  ABSORPTION AND SCATTERING COEFFICIENTS OF TITANIUM DIOXIDE PARTICULATE SUSPENSIONS IN WATER , 1996 .

[59]  M. Calzada,et al.  Synthesis and Electrical Characterization of Thin Films of PT and PZT Made from a Diol‐Based Sol‐Gel Route , 1996 .

[60]  Walter Z. Tang,et al.  UV/TiO2 photocatalytic oxidation of commercial dyes in aqueous solutions , 1995 .

[61]  B. Claudel,et al.  On the “immobilization” of titanium dioxide in the photocatalytic oxidation of spent waters , 1995 .

[62]  S. Boyd,et al.  Cationic Surfactant Adsorption by Swelling and Nonswelling Layer Silicates , 1995 .

[63]  J. Yates,et al.  Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results , 1995 .

[64]  Nick Serpone,et al.  Photocatalyzed destruction of water contaminants , 1991 .

[65]  A. L. Patterson.  The Scherrer Formula for X-Ray Particle Size Determination , 1939 .

[66]  Han Gao,et al.  Free-Standing Porous Anodic Alumina Templates for Atomic Layer Deposition of Highly Ordered TiO2 Nanotube Arrays on Various Substrates , 2008 .

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

[68]  H. Kozuka,et al.  PVP-assisted sol-gel deposition of single layer ferroelectric thin films over submicron or micron in thickness , 2004 .

[69]  Sung-Chul Kim,et al.  Photocatalytic oxidation of microcystin-LR in a fluidized bed reactor having TiO2-coated activated carbon , 2004 .

[70]  E. McFarland,et al.  Automated electrochemical synthesis and characterization of TiO2 supported Au nanoparticle electrocatalysts , 2004 .

[71]  Jiaguo Yu,et al.  Effect of surface microstructure on the photoinduced hydrophilicity of porous TiO2 thin films , 2002 .

[72]  C. Sanchez,et al.  Interactions between poly(ethylene oxide)-based surfactants and transition metal alkoxides: their role in the templated construction of mesostructured hybrid organic–inorganic composites , 2000 .

[73]  Keiichi Tanaka,et al.  Photocatalytic degradation of commercial azo dyes , 2000 .

[74]  A. Salinaro,et al.  RELATIVE PHOTONIC EFFICIENCIES AND QUANTUM YIELDS IN HETEROGENEOUS PHOTOCATALYSIS . PART I : SUGGESTED , 1999 .

[75]  Y. Torii,et al.  Morphology of thin anatase coatings prepared from alkoxide solutions containing organic polymer, affecting the photocatalytic decomposition of aqueous acetic acid , 1995, Journal of Materials Science.