Solvothermal synthesis of mesoporous TiO2: The effect of morphology, size and calcination progress on photocatalytic activity in the degradation of gaseous benzene

Abstract The photocatalytic activity of a mesoporous anatase TiO 2 catalyst, which was prepared using a solvothermal method, was studied for the degradation of gaseous benzene under UV irradiation. The optimal synthesis conditions, which utilised acetic acid/butyl titanate (5:1 v/v) with calcination at 400 °C, were determined, and nanopores in the prepared samples were found. The newly prepared TiO 2 powders were characterised using X-ray diffractometer (XRD), scanning electronic microscopy (SEM), Brunauer–Emmett–Teller (BET) N 2 adsorption, transmission electronic microscopy (TEM) and high resolution transmission electronic microscopy (HRTEM). The effects of the different morphologies, sizes and calcination temperatures on the photocatalytic activity of the prepared samples were discussed in detail. Nano-sized TiO 2 particles that were synthesised under optimal conditions show the largest specific surface area (130.3 m 2 /g), which is nearly two times that of Degussa P25. These particles also have the highest efficiency, which is significantly higher than was observed with Degussa P25. A modified Langmuir–Hinshelwood kinetic model was used considering a pseudo-steady state approach in order to explain the dependence of the apparent reaction rate constant and the apparent Langmuir adsorption constant on light intensity. Different intermediates in the samples used during the photocatalytic degradation of benzene have been identified using GC–MS analysis. A detailed reaction mechanism is proposed to explain their formation.

[1]  N. Serpone,et al.  Subnanosecond Relaxation Dynamics in TiO2 Colloidal Sols (Particle Sizes Rp = 1.0-13.4 nm). Relevance to Heterogeneous Photocatalysis , 1995 .

[2]  G. Ungváry,et al.  Embryotoxic effects of benzene and its methyl derivatives: toluene, xylene. , 1978, Toxicology.

[3]  P. Guyot-Sionnest,et al.  Synthesis and Characterization of Strongly Luminescing ZnS-Capped CdSe Nanocrystals , 1996 .

[4]  Jun Ma,et al.  Hydrothermal synthesis of TiO2 hollow microspheres for the photocatalytic degradation of 4-chloronitrobenzene. , 2010, Journal of hazardous materials.

[5]  Xianzhi Fu,et al.  Degradation of benzene over a zinc germanate photocatalyst under ambient conditions. , 2008, Environmental science & technology.

[6]  Teng Zhai,et al.  Hydrogenated TiO2 nanotube arrays for supercapacitors. , 2012, Nano letters.

[7]  Cláudia G. Silva,et al.  Effect of key operational parameters on the photocatalytic oxidation of phenol by nanocrystalline sol–gel TiO2 under UV irradiation , 2009 .

[8]  R. Amal,et al.  Selective synthesis of TiO2-based nanoparticles with highly active surface sites for gas-phase photocatalytic oxidation , 2013 .

[9]  Yunfeng Lu,et al.  Mesoporous titania spheres with tunable chamber stucture and enhanced photocatalytic activity. , 2007, Journal of the American Chemical Society.

[10]  S. Mullens,et al.  Hydrothermal synthesis of a concentrated and stable dispersion of TiO2 nanoparticles , 2013 .

[11]  J. Raulin,et al.  Heterogeneous photocatalysis: state of the art and present applications In honor of Pr. R.L. Burwell Jr. (1912–2003), Former Head of Ipatieff Laboratories, Northwestern University, Evanston (Ill). , 2005 .

[12]  M. Salavati‐Niasari Controllable synthesis of thioglycolic acid capped ZnS(Pn)0.5 nanotubes via simple aqueous solution , 2010 .

[13]  Ilkeun Lee,et al.  Control of the nanoscale crystallinity in mesoporous TiO2 shells for enhanced photocatalytic activity , 2012 .

[14]  Wen Chen,et al.  Hydrothermal synthesis of porous TiO2 microspheres and their photocatalytic degradation of gaseous benzene , 2011 .

[15]  B. Ohtani,et al.  Novel synthesis of microcrystalline titanium(IV) oxide having high thermal stability and ultra-high photocatalytic activity: thermal decomposition of titanium(IV) alkoxide in organic solvents , 1997 .

[16]  Mietek Jaroniec,et al.  Tunable photocatalytic selectivity of hollow TiO2 microspheres composed of anatase polyhedra with exposed {001} facets. , 2010, Journal of the American Chemical Society.

[17]  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.

[18]  Z. Baolong Preparation and characterization of nanocrystal grain TiO2 porous microspheres , 2003 .

[19]  Dionysios D. Dionysiou,et al.  Evaluating the activities of immobilized TiO2 powder films for the photocatalytic degradation of organic contaminants in water , 2004 .

[20]  D. Wolbert,et al.  Gas phase photocatalysis and liquid phase photocatalysis: Interdependence and influence of substrate concentration and photon flow on degradation reaction kinetics , 2008 .

[21]  Dionysios D. Dionysiou,et al.  TiO2 photocatalyst for indoor air remediation: Influence of crystallinity, crystal phase, and UV radiation intensity on trichloroethylene degradation , 2010 .

[22]  M. Seery,et al.  A review on the visible light active titanium dioxide photocatalysts for environmental applications , 2012 .

[23]  E. Stathatos,et al.  Effect of surfactant in a modified sol on the physicochemical properties and photocatalytic activity of crystalline TiO2 nanoparticles , 2007 .

[24]  D. Dionysiou,et al.  TiO2 photocatalytic films on stainless steel: The role of Degussa P-25 in modified sol–gel methods , 2006 .

[25]  Dionysios D. Dionysiou,et al.  A COMPARATIVE STUDY ON PHYSICOCHEMICAL PROPERTIES AND PHOTOCATALYTIC BEHAVIOR OF MACROPOROUS TIO2-P25 COMPOSITE FILMS AND MACROPOROUS TIO2 FILMS COATED ON STAINLESS STEEL SUBSTRATE , 2007 .

[26]  Xiaowei Zhao,et al.  Nanoporous anatase TiO2 mesocrystals: additive-free synthesis, remarkable crystalline-phase stability, and improved lithium insertion behavior. , 2011, Journal of the American Chemical Society.

[27]  D. Ollis,et al.  Kinetics of liquid phase semiconductor photoassisted reactions: supporting observations for a pseudo-steady-state model. , 2006, The journal of physical chemistry. B.

[28]  Elias Stathatos,et al.  Photocatalytic TiO2 films and membranes for the development of efficient wastewater treatment and reuse systems , 2007 .

[29]  E. Teller,et al.  On a Theory of the van der Waals Adsorption of Gases , 1940 .

[30]  D. Kuang,et al.  Effect of TiO2 morphology on photovoltaic performance of dye-sensitized solar cells: nanoparticles, nanofibers, hierarchical spheres and ellipsoid spheres , 2012 .

[31]  D. Murzin Heterogeneous  photocatalytic  kinetics: beyond the adsorption/desorption equilibrium concept , 2006 .

[32]  Sun-Jae Kim,et al.  Preparation of Ultrafine Crystalline TiO2 Powders from Aqueous TiCl4 Solution by Precipitation , 1998 .

[33]  J. Herrmann,et al.  PHOTOCATALYTIC DEGRADATION OF VARIOUS TYPES OF DYES (ALIZARIN S, CROCEIN ORANGE G, METHYL RED, CONGO RED, METHYLENE BLUE) IN WATER BY UV-IRRADIATED TITANIA , 2002 .

[34]  S. Komarneni,et al.  Palygorskite- and Halloysite-TiO2 nanocomposites: Synthesis and photocatalytic activity , 2010 .

[35]  Xingyi Deng,et al.  Gas-phase photo-oxidation of organic compounds over nanosized TiO2 photocatalysts by various preparations , 2002 .

[36]  D. Ollis Kinetic Disguises in Heterogeneous Photocatalysis , 2005 .

[37]  Louis E. Brus,et al.  Nucleation and Growth of CdSe on ZnS Quantum Crystallite Seeds and Vice Versa, in Inverse Micelle Media , 1990 .

[38]  Jiaguo Yu,et al.  EFFECTS OF HYDROTHERMAL TEMPERATURE AND TIME ON THE PHOTOCATALYTIC ACTIVITY AND MICROSTRUCTURES OF BIMODAL MESOPOROUS TIO2 POWDERS , 2007 .

[39]  Qiuyun Zhang,et al.  Photocatalytic Ozonation of Dimethyl Phthalate over TiO2 Prepared by a Hydrothermal Method , 2010, 2010 4th International Conference on Bioinformatics and Biomedical Engineering.

[40]  Young Ku,et al.  Photocatalytic degradation of gaseous benzene in air streams by using an optical fiber photoreactor , 2003 .

[41]  Z. Li,et al.  Nanocrystalline Ternary Wide Band Gap p-Block Metal Semiconductor Sr2Sb2O7: Hydrothermal Syntheses and Photocatalytic Benzene Degradation , 2008 .

[42]  Z. Dong,et al.  Hierarchical TiO2 nanoflakes and nanoparticles hybrid structure for improved photocatalytic activity , 2012 .

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

[44]  D. Ollis Kinetics of liquid phase photocatalyzed reactions: An illuminating approach. , 2005, The journal of physical chemistry. B.

[45]  J. Herrmann,et al.  HETEROGENEOUS PHOTOATALYSIS: STATE OF THE ART AND PRESENT APPLICATIONS , 2005 .

[46]  Danzhen Li,et al.  Microwave hydrothermal synthesis of calcium antimony oxide hydroxide with high photocatalytic activity toward benzene. , 2009, Environmental science & technology.

[47]  Koichi Niihara,et al.  Formation of titanium oxide nanotube , 1998 .

[48]  D. Marchisio,et al.  Synthesis, characterization, and photocatalytic application of novel TiO2 nanoparticles. , 2010 .

[49]  D. Blake,et al.  Heterogeneous Photocatalysis for Control of Volatile Organic Compounds in Indoor Air. , 1996, Journal of the Air & Waste Management Association.

[50]  Yuhan Sun,et al.  A Simple Non‐Aqueous Route to Anatase TiO2 , 2008 .

[51]  P. Praserthdam,et al.  Effect of crystallite size on the surface defect of nano-TiO2 prepared via solvothermal synthesis , 2006 .

[52]  J. M. Doña-Rodríguez,et al.  Photocatalytical removal of bentazon using commercial and sol–gel synthesized nanocrystalline TiO2: Operational parameters optimization and toxicity studies , 2012 .

[53]  P. Fang,et al.  Effective removal of high-chroma crystal violet over TiO2-based nanosheet by adsorption–photocatalytic degradation , 2012 .

[54]  A. Fujishima,et al.  Electrochemical Photolysis of Water at a Semiconductor Electrode , 1972, Nature.

[55]  S. Komarneni,et al.  Halloysite–TiO2 nanocomposites: Synthesis, characterization and photocatalytic activity , 2013 .

[56]  Jackie Y. Ying,et al.  Role of Particle Size in Nanocrystalline TiO2-Based Photocatalysts , 1998 .

[57]  L. Kavan,et al.  Mesoporous electrode material from alumina-stabilized anatase TiO2 for lithium ion batteries , 2005 .

[58]  Zhonghua Deng,et al.  Application of titanate nanoflowers for dye removal: A comparative study with titanate nanotubes and nanowires , 2012 .

[59]  A. Emeline,et al.  Factors affecting the efficiency of a photocatalyzed process in aqueous metal-oxide dispersions: Prospect of distinguishing between two kinetic models , 2000 .