Titanium dioxide–based nanomaterials for photocatalytic water treatment

Abstract Water treatment using photocatalysis has gained extensive attention in recent years. Photocatalysis is promising technology from green chemistry point of view. The most widely studied and used photocatalyst for decomposition of pollutants in water under ultraviolet (UV) irradiation is TiO2 because it is not toxic, relatively cheap, and highly active in various reactions. Within this thesis, unmodified and modified TiO2 materials (powders and thin films) were prepared. Physicochemical properties of photocatalytic materials were characterized with UV-visible spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, ellipsometry, time-of-flight secondary ion mass spectrometry, Raman spectroscopy, goniometry, diffuse reflectance measurements, thermogravimetric analysis, and nitrogen adsorption/desorption. Photocatalytic activity of prepared samples in aqueous environment was tested using model compounds such as phenol, formic acid, and metazachlor. In addition, purification of real pulp and paper wastewater effluent was studied. Concentration of chosen pollutants was measured with high-performance liquid chromatography. Mineralization and oxidation of organic contaminants were monitored with total organic carbon (TOC) and chemical oxygen demand (COD) analysis. Titanium dioxide powders prepared via sol–gel method and doped with dysprosium and praseodymium were photocatalytically active for decomposition of metazachlor. The highest degradation rate of metazachlor was observed when Pr-TiO2 treated at 450°C (8 h) was used. The photocatalytic light-emitting diode–based treatment of wastewater effluent from plywood mill using commercially available TiO2 was demonstrated to be promising posttreatment method (72% of COD and 60% of TOC was decreased after 60 min of irradiation). The TiO2 coatings prepared by atomic layer deposition technique on aluminum foam were photocatalytically active for degradation of formic and phenol; however, suppression of activity was observed. Photocatalytic activity of TiO2/SiO2 films doped with gold bipyramid-like nanoparticles was about two times higher than reference, which was not the case when gold nanospheres were used.

[1]  N. Tohge,et al.  A Patterned-TiO 2 /SnO 2 Bilayer Type Photocatalyst , 2000 .

[2]  M. Sillanpää,et al.  Removal of recalcitrant contaminants from bleaching effluents in pulp and paper mills using ultrasonic irradiation and Fenton-like oxidation, electrochemical treatment, and/or chemical precipitation: A comparative study , 2010 .

[3]  P. V. Varde,et al.  Light emitting diodes reliability review , 2012, Microelectron. Reliab..

[4]  James A. Schwarz,et al.  Methods for Preparation of Catalytic Materials , 1995 .

[5]  Didier Robert,et al.  Bi2S3/TiO2 and CdS/TiO2 heterojunctions as an available configuration for photocatalytic degradation of organic pollutant , 2004 .

[6]  R. Hennig,et al.  Computational Screening of 2D Materials for Photocatalysis. , 2015, The journal of physical chemistry letters.

[7]  Carl Brännlund,et al.  Silica hybrid sol-gel materials with unusually high concentration of Pt-organic molecular guests: studies of luminescence and nonlinear absorption of light. , 2012, ACS applied materials & interfaces.

[8]  Suljo Linic,et al.  Predictive Model for the Design of Plasmonic Metal/Semiconductor Composite Photocatalysts , 2011 .

[9]  Z. Šaponjić,et al.  Elongated titania nanostructures as efficient photocatalysts for degradation of selected herbicides , 2014 .

[10]  J. Herrmann.  Fundamentals and misconceptions in photocatalysis , 2010 .

[11]  Zhenhua Jiao,et al.  Regeneration of nano-ZnO photocatalyst by the means of soft-mechanochemical ion exchange method. , 2009, Journal of environmental sciences.

[12]  D. Das,et al.  Physico-chemical characterization and photocatalytic activity of zinc oxide prepared by various methods. , 2006, Journal of colloid and interface science.

[13]  A. Reller,et al.  Photoinduced reactivity of titanium dioxide , 2004 .

[15]  B. Ohtani.  Photocatalysis A to Z—What we know and what we do not know in a scientific sense , 2010 .

[16]  M. Hoffmann,et al.  Quantum Yields of the Photocatalytic Oxidation of Formate in Aqueous TiO_2 Suspensions under Continuous and Periodic Illumination , 2001 .

[17]  Virendra Kumar Saharan,et al.  Advanced Oxidation Technologies for Wastewater Treatment: An Overview , 2014 .

[18]  Anita Rachel,et al.  Comparison of photocatalytic efficiencies of TiO2 in suspended and immobilised form for the photocatalytic degradation of nitrobenzenesulfonic acids , 2002 .

[19]  B. Ohtani,et al.  What Are Titania Photocatalysts?―An Exploratory Correlation of Photocatalytic Activity with Structural and Physical Properties , 2010 .

[20]  Andrzej Sobczynski,et al.  Phenol destruction by photocatalysis on TiO2: an attempt to solve the reaction mechanism , 2004 .

[21]  M. S. Hegde,et al.  Solar photocatalytic degradation of dyes: high activity of combustion synthesized nano TiO2 , 2004 .

[22]  J. Je,et al.  Enhanced photocatalysis, colloidal stability and cytotoxicity of synchrotron X-ray synthesized Au/TiO2 nanoparticles , 2009 .

[23]  N. Herlin‐Boime,et al.  One step synthesis of N-doped and Au-loaded TiO2 nanoparticles by laser pyrolysis: Application in photocatalysis , 2015 .

[24]  Robert P. Fishwick,et al.  Optimisation of degradation conditions of 1,8-diazabicyclo[5.4.0]undec-7-ene in water and reaction kinetics analysis using a cocurrent downflow contactor photocatalytic reactor , 2007 .

[25]  Yong‐Mook Kang,et al.  Rational design of 3D dendritic TiO2 nanostructures with favorable architectures. , 2011, Journal of the American Chemical Society.

[26]  L. Gao,et al.  Preparation of nanosized titania by hydrolysis of alkoxide titanium in micelles , 2002 .

[27]  L. Palmisano,et al.  Characterization and photoactivity of coupled ZnO–ZnWO4 catalysts prepared by a sol–gel method , 2014 .

[28]  J. Herrmann,et al.  Photocatalysis fundamentals revisited to avoid several misconceptions , 2010 .

[29]  B. Ohtani.  Photocatalysis by Inorganic Solid Materials: Revisiting Its Definition, Concepts, and Experimental Procedures , 2011 .

[30]  S. Nair,et al.  Photocatalytic Water Treatment by Titanium Dioxide: Recent Updates , 2012 .

[31]  K. Johnston,et al.  Synthesis of TiO2 nanoparticles utilizing hydrated reverse micelles in CO2. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[32]  B. Ohtani,et al.  Correlation between Photocatalytic Activities and Structural and Physical Properties of Titanium(IV) Oxide Powders , 2009 .

[33]  Suraya Abdul Rashid,et al.  Immobilisation of titanium dioxide onto supporting materials in heterogeneous photocatalysis: A review , 2010 .

[34]  Mikko Ritala,et al.  Atomic Layer Deposition of Photocatalytic TiO2 Thin Films from Titanium Tetramethoxide and Water , 2004 .

[35]  Eiichi Kojima,et al.  Light-induced amphiphilic surfaces , 1997, Nature.

[36]  Zhen Ma,et al.  Design of Novel Structured Gold Nanocatalysts , 2011 .

[37]  Mikko Heikkilä,et al.  Effect of thickness of ALD grown TiO2 films on photoelectrocatalysis , 2009 .

[38]  Yi Zheng,et al.  BiVO4/TiO2 nanocrystalline heterostructure: A wide spectrum responsive photocatalyst towards the highly efficient decomposition of gaseous benzene , 2011 .

[39]  A. Ghorbel,et al.  Effect of Na content and thermal treatment of titanate nanotubes on the photocatalytic degradation of formic acid , 2013 .

[40]  Swagata Banerjee,et al.  Self-Cleaning Applications of TiO2 by Photo-Induced Hydrophilicity and Photocatalysis , 2015 .

[41]  G. Marin,et al.  TiO2 thin films for photocatalytic applications , 2009 .

[42]  A. Fujishima,et al.  Applications of TiO2 Photocatalysis , 2002 .

[43]  José Antonio Ayllón,et al.  TIO2-photocatalyzed degradation of phenol and ortho-substituted phenolic compounds , 2001 .

[44]  Akira Fujishima,et al.  Titanium dioxide photocatalysis , 2000 .

[45]  D. Robert,et al.  Photocatalytic degradation of the diuron pesticide , 2008 .

[46]  G. Tyuliev,et al.  Influence of the size of gold nanoparticles deposited on TiO2 upon the photocatalytic destruction of oxalic acid , 2007 .

[47]  Jin Ho Song,et al.  Application of cold crucible for melting of UO2/ZrO2 mixture , 2003 .

[48]  R. L. Sawhney,et al.  Treatment of Hazardous Organic and Inorganic Compounds through Aqueous-Phase Photocatalysis: A Review , 2004 .

[49]  Roberto Andreozzi,et al.  Advanced oxidation processes (AOP) for water purification and recovery , 1999 .

[50]  A. Baruah,et al.  Design of porous silica supported tantalum oxide hollow spheres showing enhanced photocatalytic activity. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[51]  B. Ohtani,et al.  Is methylene blue an appropriate substrate for a photocatalytic activity test? A study with visible-light responsive titania , 2006 .

[52]  Junhui He,et al.  Synthesis of raspberry-like SiO2-TiO2 nanoparticles toward antireflective and self-cleaning coatings. , 2013, ACS applied materials & interfaces.

[53]  Adriana Zaleska,et al.  Mechanism of phenol photodegradation in the presence of pure and modified-TiO2: A review. , 2012, Water research.

[54]  Sarah E. Mowry,et al.  Kinetics of Methylene Blue Reduction by Ascorbic Acid , 1999 .

[55]  A. Reinstaller.  Policy entrepreneurship in the co-evolution of institutions, preferences, and technology: Comparing the diffusion of totally chlorine free pulp bleaching technologies in the US and Sweden , 2005 .

[56]  Karuppan Muthukumar,et al.  A review on Fenton and improvements to the Fenton process for wastewater treatment , 2014 .

[57]  G Thompson,et al.  The treatment of pulp and paper mill effluent: a review. , 2001, Bioresource technology.

[58]  N. Jaffrezic‐Renault,et al.  Physicochemical properties and photocatalytic activities of TiO2-films prepared by sol–gel methods , 2002 .

[59]  T. Amemiya,et al.  Photocatalytic Activity of Sol−Gel TiO2 Thin Films on Various Kinds of Glass Substrates: The Effects of Na+ and Primary Particle Size , 2004 .

[60]  Tuqiao Zhang,et al.  Preparation of SiO2@Au@TiO2 core–shell nanostructures and their photocatalytic activities under visible light irradiation , 2013 .

[61]  A. Matsuda,et al.  Fabrication of Shape-Controlled Au Nanoparticles in a TiO2-Containing Mesoporous Template Using UV Irradiation and Their Shape-Dependent Photocatalysis , 2014 .

[62]  Göksel N. Demirer,et al.  Cleaner production opportunity assessment study in SEKA Balikesir pulp and paper mill , 2008 .

[63]  C. Pirola,et al.  Degradation of organic water pollutants through sonophotocatalysis in the presence of TiO(2). , 2003, Ultrasonics sonochemistry.

[64]  M. L. Martín-Díaz,et al.  Combined AOPs for potential wastewater reuse or safe discharge based on multi-barrier treatment (microfiltration-H2O2/UV-catalytic wet peroxide oxidation) , 2015 .

[65]  J. Herrmann,et al.  Heterogeneous photocatalysis: fundamentals and applications to the removal of various types of aqueous pollutants , 1999 .

[66]  C. Fan,et al.  Facile regeneration and photocatalytic activity of CuO-modified silver bromide photocatalyst , 2015 .

[67]  Dionysios D. Dionysiou,et al.  A Review of Solar and Visible Light Active TiO2 Photocatalysis for Treating Bacteria, Cyanotoxins and Contaminants of Emerging Concern , 2016 .

[68]  Andrew Mills,et al.  An overview of semiconductor photocatalysis , 1997 .

[69]  Chung-Yi Wu,et al.  Thickness-dependent photocatalytic performance of nanocrystalline TiO2 thin films prepared by sol–gel spin coating , 2013 .

[70]  Y. Horiuchi,et al.  Understanding TiO2 photocatalysis: mechanisms and materials. , 2014, Chemical reviews.

[71]  Mikko Heikkilä,et al.  Noble metal-modified TiO2 thin film photocatalyst on porous steel fiber support , 2010 .

[72]  Cesar Pulgarin,et al.  Effect of pH, inorganic ions, organic matter and H2O2 on E. coli K12 photocatalytic inactivation by TiO2: Implications in solar water disinfection , 2004 .

[73]  C. Guillard,et al.  Phenol photocatalytic degradation over anisotropic TiO2 nanomaterials: Kinetic study, adsorption isotherms and formal mechanisms , 2015 .

[74]  Bunsho Ohtani,et al.  Titania Photocatalysis beyond Recombination: A Critical Review , 2013 .

[75]  Ewa Kowalska,et al.  Visible-light-induced photocatalysis through surface plasmon excitation of gold on titania surfaces. , 2010, Physical chemistry chemical physics : PCCP.

[76]  Niko Suhonen,et al.  Competition in the global pulp and paper industries – An evaluation based on three approaches , 2011 .

[77]  K. Schanze,et al.  Best practices for reporting on heterogeneous photocatalysis. , 2014, ACS applied materials & interfaces.

[78]  N. Murafa,et al.  Preparation and photocatalytic activity of rare earth doped TiO2 nanoparticles , 2009 .

[79]  M. Sillanpää,et al.  Electrochemical oxidation of sulphides in paper mill wastewater by using mixed oxide anodes , 2009, Environmental technology.

[80]  Dunia E. Santiago,et al.  Photocatalytic treatment of water containing imazalil using an immobilized TiO2 photoreactor , 2015 .

[81]  Alessandro Martucci,et al.  Gold‐Nanoparticle‐Doped TiO2 Semiconductor Thin Films: Optical Characterization , 2007 .

[82]  R. Asahi,et al.  Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides , 2001, Science.

[83]  M. I. Maldonado,et al.  Regeneration approaches for TiO2 immobilized photocatalyst used in the elimination of emerging contaminants in water , 2014 .

[84]  F. Kargı,et al.  Advanced oxidation treatment of pulp mill effluent for TOC and toxicity removals. , 2008, Journal of environmental management.

[85]  D. Ollis,et al.  Catalyst Deactivation in Gas–Solid Photocatalysis , 1996 .

[86]  Adrián M.T. Silva,et al.  An overview on the advanced oxidation processes applied for the treatment of water pollutants defined in the recently launched Directive 2013/39/EU. , 2015, Environment international.

[87]  B. Ohtani.  Preparing Articles on Photocatalysis : Beyond the Illusions, Misconceptions, and Speculation , 2008 .

[88]  Dong-Wha Park,et al.  Size-dependence of plasmonic Au nanoparticles in photocatalytic behavior of Au/TiO2 and Au@SiO2/TiO2 , 2015 .

[89]  J. Nozaki,et al.  Treatment of paper pulp and paper mill wastewater by coagulation–flocculation followed by heterogeneous photocatalysis , 2008 .

[90]  S. Barry,et al.  Principles of precursor design for vapour deposition methods , 2016 .

[91]  Qiujing Yang,et al.  Effects of synthesis parameters on the physico-chemical and photoactivity properties of titania–silica mixed oxide prepared via basic hydrolyzation , 2005 .

[92]  L. Österlund,et al.  A comparative study of the photocatalytic oxidation of propane on anatase, rutile, and mixed-phase anatase–rutile TiO2 nanoparticles: Role of surface intermediates , 2007 .

[93]  Julián Blanco,et al.  Decontamination and disinfection of water by solar photocatalysis: Recent overview and trends , 2009 .

[94]  Pengfei Yang,et al.  Visible light-driven photocatalysis of W, N co-doped TiO2 , 2013 .

[95]  Parveen Kumar,et al.  Titanium dioxide photocatalysis for the pulp and paper industry wastewater treatment , 2011 .

[96]  R. Caruso,et al.  Enhancing photocatalytic activity of titania materials by using porous structures and the addition of gold nanoparticles , 2011 .

[97]  R. L. Pozzo,et al.  Towards a precise assessment of the performance of supported photocatalysts for water detoxification processes , 1999 .

[98]  E. Souaya,et al.  Treatment of highly polluted paper mill wastewater by solar photocatalytic oxidation with synthesized nano TiO2 , 2011 .

[99]  Chiing-Chang Chen,et al.  Phorate degradation by TiO2 photocatalysis: parameter and reaction pathway investigations. , 2010 .

[100]  S. Parola,et al.  Mechanically stable and photocatalytically active TiO2/SiO2 hybrid films on flexible organic substrates , 2014 .

[101]  Kimmo Silvo,et al.  Implications of regulation based on the IPPC directive – A review on the Finnish pulp and paper industry , 2009 .

[102]  K. Hashimoto,et al.  Decomposition of gas-phase octamethyltrisiloxane on TiO2 thin film photocatalysts: catalytic activity, deactivation, and regeneration , 2003 .

[103]  M. Centeno,et al.  Titania-Supported Gold Catalysts: Comparison between the Photochemical Phenol Oxidation and Gaseous CO Oxidation Performances , 2008 .

[104]  R. Kaur,et al.  Size and shape dependent attachments of Au nanostructures to TiO2 for optimum reactivity of Au–TiO2 photocatalysis , 2012 .

[105]  E. Selli,et al.  Photocatalytic degradation of formic and benzoic acids and hydrogen peroxide evolution in TiO2 and ZnO water suspensions , 2006 .

[106]  Paul Mulvaney,et al.  Effect of the Solution Refractive Index on the Color of Gold Colloids , 1994 .

[107]  Yi‐hong Ding,et al.  The Design of TiO2 Nanostructures (Nanoparticle, Nanotube, and Nanosheet) and Their Photocatalytic Activity , 2014 .

[108]  Tamara Hafner,et al.  Environmental policy vs. public pressure: Innovation and diffusion of alternative bleaching technologies in the pulp industry , 2011 .

[109]  Gang Chen,et al.  New photocatalyst BiOCl/BiOI composites with highly enhanced visible light photocatalytic performances. , 2011, Dalton transactions.

[110]  A. Pandikumar,et al.  Titanium dioxide-gold nanocomposite materials embedded in silicate sol-gel film catalyst for simultaneous photodegradation of hexavalent chromium and methylene blue. , 2012, Journal of hazardous materials.

[111]  R. M. Lambert,et al.  Enhancement of MTBE photocatalytic degradation by modification of TiO2 with gold nanoparticles , 2007 .

[112]  Ewa Kowalska,et al.  Visible light-induced photocatalytic reaction of gold-modified titanium(IV) oxide particles: action spectrum analysis. , 2009, Chemical communications.

[113]  X. Lin,et al.  Photocatalytic Activities of Heterojunction Semiconductors Bi2O3/BaTiO3: A Strategy for the Design of Efficient Combined Photocatalysts , 2007 .

[114]  M. Minella,et al.  Transformation of 2,4,6-trimethylphenol and furfuryl alcohol, photosensitised by Aldrich humic acids subject to different filtration procedures. , 2013, Chemosphere.

[115]  R. Amal,et al.  Progress in Heterogeneous Photocatalysis: From Classical Radical Chemistry to Engineering Nanomaterials and Solar Reactors. , 2012, The journal of physical chemistry letters.

[116]  Peter K. J. Robertson,et al.  Overview of the current ISO tests for photocatalytic materials , 2012 .

[117]  W. Ho,et al.  Sonochemical synthesis and visible light photocatalytic behavior of CdSe and CdSe/TiO2 nanoparticles , 2006 .

[118]  M. Anderson,et al.  Sol–gel preparation of TiO2–ZrO2 thin films supported on glass rings: Influence of phase composition on photocatalytic activity , 2006 .

[119]  D. Ollis.  Photocatalytic purification and remediation of contaminated air and water , 2000 .

[120]  R. Naidu,et al.  Tailored titanium dioxide photocatalysts for the degradation of organic dyes in wastewater treatment: A review , 2009 .

[121]  Y. Paz,et al.  Using Dyes for Evaluating Photocatalytic Properties: A Critical Review , 2014, Molecules.

[122]  C. Negro,et al.  Degradation of 1,4-dioxane from industrial wastewater by solar photocatalysis using immobilized NF-TiO2 composite with monodisperse TiO2 nanoparticles , 2016 .

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