Introduction

The presence of harmful organic compounds in water supplies and in the discharge of wastewater from chemical industries, power plants, landfills, and agricultural sources is a topic of global concern. Traditional water treatment processes include filtration and flocculation, biological treatment, thermal and catalytic oxidation, and chemical treatment using chlorine, potassium permanganate, ozone, hydrogen peroxide and high-energy ultraviolet light, [1, 2]. All these water treatment processes, currently in use, have limitations of their own and none is cost-effective: 1. Phase transfer methods remove unwanted organic pollutants from wastewater, but they do not eliminate the pollutants entirely; 2. Cost of biological treatment is low, however, some of the toxic compounds present are found to be lethal for microorganisms intended to degrade them, and there is a class of non-biodegradable organic products noted as biorecalcitrant organic compounds;
3. While chemical treatments based on aqueous phase hydroxyl radical chemistry are

powerful to oxidize toxic organic compounds present in water, these processes either use high-energy ultraviolet light or strong chemical oxidants of hazardous and therefore, undesirable nature, [3]. Moreover, several intermediates, which are more hazardous, are formed in these processes, and because of very low efficiencies, overall treatment cost becomes high if destruction of intermediates and complete mineralization are to be achieved, especially for treating dilute wastewater streams, [4]. Degradation or decomposition by photocatalysis is a novel method for the treatment of air and water pollutants, [5]. Semiconductor photocatalysis with a primary focus on TiO2 is widely used. Literature mentions that, photocatalytic processes on TiO2, under UV radiation, can be efficiently applied for the degradation of non-biodegradable azo-dyes, [6, 7, 8]. Thus, recently, TiO2 thin films have been reported as being successfully used for the photocatalytic degradation of methyl orange and methylene blue, a typical pollutants in the textile industry, [9]. Powders and thin films of titania will photodegrade a wide range of organic and inorganic chemicals in air and water. Other applications have included the elimination of microorganisms such as bacteria, viruses, cancer cells and the reduction of trace heavy metals. Photocatalysis requires large values of the specific surface; therefore TiO2 powder is usually used as provided or as thin film. Several practical problems arising from the use of powder are obvious during the photocatalytic process:

separation of the insoluble catalyst from the suspension is difficult, the suspended particles tend to aggregate especially at high concentrations, suspensions are difficult to apply to continuous flow systems. The photocatalytic activity of TiO2 in UV spectral regions is highly dependent on the

preparation method [10]. There are a number of methods which can be used to obtain the TiO2 films, including: doctor blade [11], spray coating, dip coating [12], spin coating [13], chemical vapour deposition [14]. Dip coating it is an attractive method to prepare a wide variety of powders and thin film materials for various industrial applications (solar cell, photodegradation, gas sensor)[15]. Modifications in the catalyst surface have also been investigated for prevention of electron-hole recombination. The addition of platinum and other transition metals have been successfully arrayed on the titanium dioxide surface. These metal additions have an optimum at low weight percentages (less than 5%), above which the metal actually hinders the photocatalytic ability.

Fundamentals
Wastewater; Industrial wastewater; Wastewaters from the textile industry Our biosphere is under constant threat from continuing environmental pollution. Impact on its atmosphere, hydrosphere and lithosphere by anthropogenic activities can not be ignored. Man made activities on water by domestic, industrial, agriculture, shipping, radioactive, aquaculture wastes; on air by industrial pollutants, mobile combustion, burning of fuels, agricultural activities, ionization radiation, cosmic radiation, suspended particulate matter; and on land by domestic wastes, industrial waste, agricultural chemicals and fertilizers, acid rain, animal waste have negative influence over biotic and abiotic components on different natural ecosystems. Some of the recent environmental issues include green house effect, loss in bio-diversity, rising of sea level, abnormal climatic change and ozone layer depletion etc.. The industrial wastewater is discharged with pre-treatment or neutralization either to municipal sewers that flow into rivers or directly into rivers without pretreatment or neutralization. The water quality of nearby river water is deteriorated by this direct discharge of the raw effluent from the industry, which renders to reduce the aesthetic value as well as the aquatic ecosystem hamper. In recent years, different approaches have been discussed to tackle man made environmental hazards. Clean technology, eco-mark and green chemistry are some of the most highlighted practices in preventing and or reducing the adverse effect on our surroundings. Among many engineering disciplines Civil Engineering, Mechanical Engineering, Electrical Engineering etc., Textile Engineering has a direct connection with environmental aspects to be explicitly and abundantly considered. Out of various activities in textile industry, chemical processing contributes about 70% of pollution. It is well known that cotton mills consume large volume of water for various processes such as sizing, desizing, scouring, bleaching, mercerization, dyeing, printing, finishing and ultimately washing. Due to the nature of various chemical processing of textiles, large volumes of waste water with numerous pollutants are discharged. Since these streams of water affect the aquatic ecosystem in number of ways such as depleting the dissolved oxygen content or settlement of suspended substances in anaerobic condition, a special attention needs to be paid [16].

Large volume wastes from textile mill include wastewater from the preparation of the substrate, rinsing and washing after dyeing operations and waste from batch dyeing operations. These wastes are not only heavily contaminated but can put a burden on the hydraulic load of the treatment system. More than 10 000 dyes are used in the textile industry and 280 000 tonnes of textile dyes are discharged every year world wide. Textile dyeing and finishing processes produce large quantities of wastewater that is highly coloured and contains large concentration of organic matter, which is difficult to treat via classical methods. Apart from the aesthetic problems created when coloured effluents reach the natural water currents, dyes strongly absorb sunlight, thus impeding the photosynthetic activity of aquatic plants and seriously threatening the whole ecosystem [17]. Sources and Causes of Generation of Textile Effluent Textile industry involves wide range of raw materials, machineries and processes to engineer the required shape and properties of the final product. Waste stream generated in this industry is essentially based on water-based effluent generated in the various activities of wet processing of textiles. The main cause of generation of this effluent is the use of huge volume of water either in the actual chemical processing or during re-processing in preparatory, dyeing, printing and finishing. In fact, in a practical estimate, it has been found that 45% material in preparatory processing, 33% in dyeing and 22% are re-processed in finishing [18]. Table 1.1.1. Properties of Waste Water from Textile Chemical Processing Property pH BOD,mg/l, 5 days COD,mg/l, day TDS, mg/l Standard 5.5-9 30-350 250 2100 Cotton 8-12 150-750 200-2400 2100-7700 Synthetic 7-9 150-200 400-650 1060-1080 Wool 3-1 5000-8000 10000-20000 10000-13000

Effluents treatment plants are the most widely accepted approaches towards achieving environmental safety. But, unfortunately, no single treatment methodology is suitable or universally adoptable for any kind of effluent treatment. For instance, in the past, biological treatment systems had been used extensively but they are not efficient for the colour removal of the more resistant dyes. Therefore, the treatment of waste stream is done by various methods, which include physical, chemical and biological treatment depending on pollution load. The treatment processes may be categorized into preliminary, primary, secondary and tertiary treatment process [1]. Various operations in each category are described below in Table 1.1.2

Table 1.1.2. Classification of waste water treatment process Treatment Primary Secondary Tertiary Operations Screening, Sedimentation, Equalization, Neutralisation Mechanical Flocculation and Chemical coagulation Aerated lagoon, Trickling filtration, Activated sludge process Oxidation ditch and pond, Anaerobic digestion Oxidation technique, Electrolytic precipitation and Foam fractionation Membrane technologies, Electrochemical processes Ion exchange method, Photo- catalytic degradation Adsorption (Activated Carbon etc.), Thermal evaporation

The choice of the method for effluent treatment depends upon four factors: effluent quantity; concentration in pollutants; quality conditions imposed for the treated water; and finance available to the organization. The wastewater treatment process used to degrease the pollution loads of industrial wastewater can be classified by many criteria, including the collection disposal and treatment process of these waters. Irrespective of the processes that are used, the industrial wastewater treatment has the following objectives: to remove the pollutants or the substances that can be the further reduced with the final effect to obtain a treated effluent that can be reintroduced in its natural circuit, recycled in technological processes or reused for different purposes (aquifers loading, dual systems for water supply, irrigation); processing of the sludge resulted from the industrial wastewater treatment. The advanced treatment is used to increase the degree of purification and to eliminate the priority pollutants that are partly removed by conventional treatment processes (colloids, nonbiodegradable organic compounds, inorganic toxic compounds, pathogen microorganisms). Advanced treatment may be applied before or after the biological processes as requested by the characteristics of the influent wastewater and the required degree of purification [19]. Advances wastewater treatment for industrial process The treatment of spent dye wastewater effluent is a growing concern for the textile industry because of aesthetic conditions, as well as ecotoxicological issues regarding colored rinsing and process wastewater and the impact of that wastewater on the receiving streams. As regulations become more stringent, the effectiveness and cost of treatment processes becomes more significant. Conventional biological treatment can be ineffective for color removal, but chemical oxidative processes seem to provide an opportunity for future use in industrial wastewater [20]. The presence of organic dyes in textile wastewater- these dyes are synthetic and non-biodegradable so, biological treatment of wastewater alone is usually not effective waters may result in poor water quality [21].

Table 1.2.1 Advanced wastewater process Process Adsorbtion (activated carbon, silica, fly ash) Ion exchange Reverse Osmosis Membrane Filtration Ultrafiltration Ozonation Multiple effect evaporation Evaporation Direct contact evaporation Crystallization Specific Treatments References [22] [23] [24] [25] [26] [27] [28] [29] [30]

However, none of these treatment methods is effective enough to produce water with acceptable levels of the most persistent pollutants (e.g., phenols, pesticides, dyes, solvents, household chemicals and drugs, etc.). A further treatment stage is often necessary to attain this objective. This stage can entail the application of advanced oxidation processes (AOPs), which are recommended when wastewater components have a high chemical stability and/or low biodegradability [2]. Advanced oxidation process In recent decades, very severe regulations have forced researchers to develop and evolve novel technologies to accomplish higher mineralization rate with lower amount of detectable contaminants. Different physical, chemical, and biological treatment processes have been employed to treat various municipal and industrial wastewaters such as chemical [31],[32], biological, food [33], pharmaceutical [34], [35], pulp and paper [36], dye processing and textile [37], [38], [39], [40], and landfill leachate [41], effluents. Advanced oxidation process (AOPs) are defined as near ambient temperature and pressure water treatment processes which are based on the generation of hydroxyl radicals to initiate oxidative destruction of organics. The hydroxyl radical is a powerful, non-selective chemical oxidant (Table I.4.) which reacts typically a million to a billion times faster that ozone and hydrogen peroxide resulting in reduced treatment costs and system size. Table 1.2.1.1 Oxidizing potential for conventional oxidizing agents Oxidizing agent Fluorine Hydroxyl radical Atomic oxygen Ozone Hydrogen peroxide Electrochemical oxidation potential (EOP), V 3.06 2.80 2.42 2.08 1.78 EOP relative to chlorine 2.25 2.05 1.78 1.52 1.30

Hypochlorite Chlorine Chlorine dioxide Oxygen molecular

1.49 1.36 1.27 1.23

1.10 1.00 0.93 0.90

AOPs used for the treatment of wastewater are based on:

Ozone (O3); Hydrogen Peroxide (H2O2);

Ozone + Hydrogen Peroxide; Fentons Reaction, Photo Fenton Process;

Photo- oxidation: UV+Ozone+H2O2, UV+H2O2

Photo- catalysis : UV+TiO2

Ozone The half-life of ozone in industrial wastewater can be expected to vary from less than a minute to up 30 min, depending on the types and ozone-reactivity of the pollutants as well as upon pH. As the pH rises, the decomposition rate of ozone in water increases. Ozone and hydrogen peroxide At lower pH addition of hydrogen peroxide at O3/H2O2- ratio of 2:1 to ozonation processes accelerates the decomposition of ozone resulting in the increased formation of hydroxyl radicals. At a concentration of hydrogen peroxide above 10-7 M and a pH- value less than 12, hydrogen peroxide reacts with ozone as the anion HO2- producing two hydroxyl radicals from two ozone molecules. Photo-oxidation Completion of oxidation reactions, as well as oxidative destruction of compounds immune to ozone or hydrogen peroxide oxidation alone, can be obtained by supplementing the reaction with ultraviolet radiation. More importantly, UV radiation accelerates the decomposition of ozone and hydrogen peroxide molecules. Although photochemical cleavage of H 2O2 is conceptionally the simplest method for hydroxyl radical production, the exceptionally low molecular absorptivity of H2O2 at 254 nm limits the yield of hydroxylic radicals in the solution. Fentons Reaction, Photo Fenton process Since hydrogen peroxide does not absorb significantly beyond 300 nm and absorbs only weakly in the range of 200-300 nm, the UV/H2O2 process is often not suitable for the treatment of polluted water with a high UV absorbance and/or a high background of total

organic carbon concentration. The oxidizing species in this reaction is again the hydroxylic radical formed according to: (1) Photocatalysis In photocatalysis, UV radiation is used to excite a solid-state metal catalyst creating a positive and negative change (electro-hole, e- h+ pairs) on the catalysts surface. These positive and negative charges promote redox reactions, e.g. oxidation of organics in the solution by the ions or oxygen by the photogenerated negative charges. Titanium dioxide is the preferred catalyst for photocatalysis due to its stability under various conditions, its high potential to produce radicals and its easy availability and low price [42]. AOPs can often achieve oxidative destruction of compounds refractory to conventional ozone or hydrogen peroxide oxidation. In addition, AOPs have the potential to completely oxidize (mineralize) organic contaminants to carbon dioxide, water and mineral salts. AOPs are suited for destroying dissolved organic contaminants such as halogenated hydrocarbons, aromatic compounds, phenols, dyes and pesticides. Therefore, AOPs show promise for destruction of hazardous organic compounds in water without generating secondary pollution commonly associated with conventional treatment technologies [42]. Heterogeneous photocatalysis Heterogeneous photocatalysis has been examined and explored extensively as a potentially viable alternative technology to classical "best" technologies for both environmental detoxification and for energy production [43].This techology employs illuminated semiconductor particulate materials, TiO2, as photocatalysts to produce both reducing and highly oxidizing species on the particle surface poised to unleash redox processes in aqueous media, many of which would not otherwise be possible by normal chemical means. The term photocatalyis is composed of the combination of photochemistry and catalysis what suggest that the light and catalyst are necessarily to drive or to accelerate a chemical transformation [44]. The activation way of the catalyst differs slightly from classical catalysis, because the thermal activation is replaced by photonic activation [45]. Nevertheless, the term photocatalysisis still disputable among scentists [46]. Serpone and Emeline took an effort to systematized the definitions and terminology related to the photocatalysis [47].

Fig. 1.2.2.1. The definition and the schema of catalysed photolysis (left) and photogenerated catalysis (right) They classified the catalytic reactions, which are driven by interaction with a light as:
a)

Catalysed photolysis also named in the literature as catalysed photoreaction or a

photosensitization. In this process, a photon is absorbed by dye molecule (ec. 2), which transfers an electron into the conduction band of the semiconductor (ec.3) . the catalyst in this case acts as an electron-transfer mediator (ec3, ec.4) and the oxygen as an electron acceptor (ec.4, 5, 6, 7) leading to efficient separation of the injected electron and the radical cation Fig.1.2.2.1. [46], [47], [48]. The dye is decomposed in the following steps: (2) (3) (4) (5) (6) (7)
Intermediates

(8)

b)

Photogenerated catalysis is also called a sensitized photoreaction. Here, the

illuminated semiconductor absorbs a photon with energy equal or larger than its band gap energy (h Eg ). This leads to the creation of the charge caries: an electron,which is excited into the conduction band and the hole, which remains in the valence band (ec. 9). Simultaneously, a spontaneous adsorbtion of the pollutant molecules on the surface of the catalyst occurs. Whit respect to redox potential or energy level an electron transfer proceeds

towards acceptor molecules (ec. 4-7), whereas photo-holes are transferred to donors molecules (ec. 10,11). Each formed ion and radical react through the intermediate reaction into direction of the full decomposition of the pollutant molecules ( Fig. right) [46], [47], [48]. (9) (10) (11) (12) (13) (14)
Intermediates

(15)

The catalysed photolysis is mostly related to dyes photodecomposition under the solar light irradiation [48], [49], [50]. The so-called photogenerated catalysis is applied not only for the decomposition of dyes but also for mineralization of many groups of organic pollutants (Tab. 1.2.2.1). Table 1.2.2.1. General group classification of organic pollutants decomposed by photocatalysis [22]. GROUP OF ORGANICS Alkanes Aliphatic carboxylic acids Alkenes Aromatics Phenolic compounds Halophenols Surfactants Herbicides Pesticides Dyes EXAMPLES isobutene, pentane, heptanes, cyclohexane, paraffins formic,ethanoic, propanoic, oxalic, butyric, malic acids propene, cyclohexene benzene, naphtalene Phenol, hydroquinone, catechol, methylcatechol, resorcinol 2-,3-,4-chlorophenol, pentachlorophenol, 4- fluorophenol sodium dodecylsulphate, polyethylene glycol, sodium dodecylbenzene sulphonate, trimethyl phosphate, atrazine, prometron, propetryne, bentazon DDT, parathion, lindane, tetrachlorvinphos, phenitrothion methylene blue, rhodamine B, methyl orange, fluorescein

In this type of process, the semiconductor plays the main role and its photocatalytic activity, which can be modified during the production step. In the photogenerated catalysis the efficiency of the process can be improved by enhancement of the photoactivity of the photocatalyst. The reactive species in n-type of semiconductors are photogenerated holes. These kind of materials are most often applied as a photocatalyst thanks to their stability against photo-corrosion (ec. 10-12). Oxygen performs in this case as an electron scavenger, stabilize the primary photo-oxidation reactions and increase the oxidation yield (ec. 5-7)

therefore presence of oxygen is necessarily to enhanced the efficiency of the photooxidation process [51]. The role of the holes in the photocatalytic process can be explained in two ways:

The holes react over indirect oxidation via a surface-bond hydroxyl radical mechanism (ec. 16) [52], [53]; The holes react over direct oxidation via the valence band holes [54].

So far, first proposed interpretation has been supported by experimental data like ESR studies by Hoffman [55] and Linsebigler et al. [56] who confirmed the existence of hydroxyl and hydroperoxy radicals in aqueous solution of illuminated TiO 2. Another fact, which confirmes this statement, is the presence of intermediates of typical hydroxylated structure during photodecomposition of halogenated aromatics in presence of TiO2 [55], [56], [57]. From the assumption that hydroxyl radicals OH- are the main oxidative species in the photocatalytic process three kinetic mechanisms of the oxidation of the organic pollutants can be proposed:

Langmuir Hinshelwood mechanism a reaction between the OH radicals at the (16)

surface of the catalyst and the adsorbed pollutant molecule (P)

Eley Rideal mechanism a reaction between the OH at the catalysts surface and (17)

the pollutant molecule in the solution

A reaction occurring between the OH in the solution and the pollutant molecule in the

solution. All three mechanisms can be expressed by the general kinetic equation: (18) where OH and pollutant molecule (P) of concentration C pollutant are adsorbed on the surface of the catalyst or are in the solution according to each mechanism [42]. . Photocatalytic materials An ideal photocatalyst for photocatalytic oxidation is characterized by the following attributes [58]: photo-stability, chemically and biologically inert nature, availibility and low cost. Many chalcogenide semiconductors such as TiO2, ZnO, ZrO2, CdS, Fe2O3 and WO3 have been examined and used as photocatalysts for the degradation of organic contaminants [59]. The minimum band gap energy required for photon to cause photogeneration of charge carriers over TiO2 semiconductor (anatase form) is 3.2 eV corresponding to wavelength of 38 8nm [60]. Actually with TiO2, photoactivation takes place in the range 300388 nm. The

photoinduced transfer of electrons that take place with adsorbed species over semiconductor photocatalyst depends on the band-edge position of the semiconductor and the redox potentials of the adsorbates [61]. In spite of the constant vigorous research activities over two decades in search for an ideal photocatalyst, titania in its anatase modification has remained a benchmark against which any emerging material candidate will be measured [62]. The anatase form of titania is reported to give the best combination of photoactivity and photostability [63].Zhang and Maggard [64], reported the preparation of hydrated form of amorphous titania with wider band energy gap than anatase and significant photocatalytic activity. The schematic diagram of band positions for various semiconductors is shown in Figure 1.3.1.

Titanium Fig.1.3.1. The conduction and valence band positions of selected metal oxide semiconductors at pH 0. The left hand scale represents the internal energies to the vacuum level. The right hand scale is the normal hydrogen electrode scale which allows predictions based on reduction and oxidation. dioxide is one of the most widely applied metal oxide thanks to its unique properties. Due to its high refractive index it is used as a pigment in the paint industry [65]. Among all properties of titanium dioxide, in the recent years the photocatalytic property is the most investigated for various applications: disinfection of the operating hospitals rooms, selfcleaning surfaces Table 1.3.1. Among them, the photodegradation of the organic pollutants (dyes) in aqueous environment is of the main interest of this work [66].

Table 1.3.1. Selected application of titanium dioxide in respect to its photoelectrochemical properties [67], [68]. PROPERTY Photocatalytic water purification Photoelectrochemical water decomposition CATEGORY Drinking water Others Hydrogen production Materials for residential and office buildings Materials for roads Indoor air cleaners Outdoor air purifiers Hospital APPLICATION River water, ground water, lakes and water storage tanks Fish feeding tanks, drain age water and industrial wastewater Fuel for automobiles sector, fuel for solid oxide fuel cell, fuel for energetic sector, for pharmaceutical and food industry Exterior tiles, kitchen and bathroom components, interior furnishing, plastic surfaces, aluminium siding, building stone and curtains, paper window blinds Tunnel hall, noise barrier, traffic signs and reflectors Room air cleaner, photocatalyst-equipped air conditioners and interior air cleaner for factories Concrete for highway, roadways and footpaths, tunnel walls, noise barriers and building walls Tiles to cover the floor and walls of operating rooms, silicone rubber for medical catheters and hospital garments and uniforms

Self-cleaning

Air cleaning

Self-sterilizing

Crystallographic structure and polymorphic forms Titanium dioxide occurs in the nature in three polymorphic forms: brookite, anatase, and rutile where the two last are commonly used in photocatalysts. Anatase and brookite as metastable phases transform to rutile in the range 973K- 1173K. The anatase to rutile transformation temperature depends on purity, type of impurities, particle shape/size, atmosphere and reaction conditions. Table 1.3.2. Basic crystallographic and physical properties of antase and rutile [69], [70]. Property Crystallographic structure Space group Anatase Tetragonal I41/amd a= 0.3784 Lattice parameters [nm] b= 0.9515 -3 3 Volume of the unit cell/molecule [10 nm ] 34.172 Density [g/cm3], T=298K 3.894 Band gap energy (Eg) [eV] 3.26 Electron effective mass (m*) 1m0 2 Hall mobility of electron [cm /Vs], T=298K 4 Rutile Tetragonal P42/mmm a= 0.4594 c= 0.2959 31.216 4.270 3.05 20m0 0.1

Basic crystallographic properties of two polymorphic forms of titanium dioxide are listed in the Table 1.3.2. [69]. Titania photocatalyst can be used either as free-standing particulate or as coating on a substrate. Most experiments utilized finely powdered TiO2 particles suspended in contaminated water, which provides large surface area and makes recovery easy after treatment [71]. Larger particulates may prove useful even in the case of gaseous organic contaminants but are rather commercially unavailable and may be costly [72].A reduction of 6070% reduction in performance is reported in aqueous systems for immobilized TiO 2 as compared to the unsupported catalyst [73]. Many kinds of support have been explored for TiO2 photocatalyst which include soda lime glass [74], aluminium [75], ceramic tiles [76] and coated glass [77]. Since coatings are very thin, the actual active surface area of the photoreactor compared to the overall volume is low. Despite aforementioned drawbacks,more coated photocatalysts and immobilisation techniques are still investigated. In many of these cases TiO2 coated on support assumed more efficiency in organic compound removal than uncoated TiO2 [78]. . Techniques for obtaining photocatalytic materials There are different routes that can be used to synthesis anatase and rutile. It has been said that the precursor and the method of preparation affect the physico-chemical properties of the synthesised particle. The routes of synthesis TiO2 used like photocatalyst include: chemical vapor deposition [79], e-beam evaporation [80], magnetron sputtering discharge [81], spray vapor deposition [82], [83], hydrothermal synthesis [84], solgel method [85], doctor blade [86]. Table 1.4.1. Routes of syntesis of titanium oxide Preparation methods Precursors The synthesis of mesoporous TiO2 was carried out with the following procedure. Four grams (0.69 mmol) of the triblock copolymer was dissolved in 100 mL of distilled water at 40C. After the surfactant had been dissolved sufficiently, 1.5 g (15.3 mmol) of sulfuric acid was added. Titanium (IV) isopropoxide (11.76 g, 41.4 mmol) was mixed with 2,4- pentanedione (4.14 g, 41.4 mmol) in a separate beaker and dropped slowly into the surfactant solution with vigorous stirring. After addition, the reaction was carried out at 55C for 2 h without stirring. At first, there was no precipitation, but after several minutes, a light yellow powder was obtained. References

Hydrotherma l method

[87]

Sol-gel synthesis

Chemical vapor deposition

Spray pyrolysis deposition

The TiO2 sol was synthesized by acid catalyzed solgel formation method using 30 ml of 1 M HNO3 and 7.4 ml of titanium tetra-isopropoxide following the hydrolysis reaction. Ti(iso-OC3H7)4+4HO Ti(OH)4+4 C3H7OH Titanium tetra-isopropoxide was added gradually to the aqueous solution of HNO3 solution under continuous stirring for 1.52 h to produce a transparent sol containing 2g of TiO2 Photocatalytic TiO2 thin film depositions were carried out in a vertical low-pressure CVD reactor. CVD reactor was home-built cold-wall type. Sources for titanium and oxygen were tetraisopropoxide and O2 gas, respectively. Deposition temperature was varied from 287C to 362C, and the processing pressure was kept at 1 Torr. The precursor solution contained titanium(IV) isopropoxide TTIP, acetylacetone (AcAc) and ethanol with TTIP concentration of 6 vol.% at TTIP:AcAc molar ratio of 1:2. The films were deposited at 300500 -C

[88]

[89]

[90]

Among the different methods (Table I.8.) for the preparation of thin films titanium dioxide for photocatalytic process, sol-gel method has many advantages, particularly the possibility of producing large surfaces [91]. Sol-Gel Methods The sol-gel process is a technique widely employed recently in the fields of materials science and ceramic engineering. Such methods are utilized primarily for the fabrication of materials (typically a metal oxide) starting from a chemical solution which acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers. Typical precursors are metal alkoxides and metal chlorides, which undergo various forms of hydrolysis and polycondensation reactions, rangind from 1 nm to 1 micrometer.

Fig. 1.4.1.1. Sol-Gel process

The formation of a metal oxide involves connecting the metal centers with either oxo (MOM) or hydroxo (MOHM) bridges, and generating metal-oxo or metal-hydroxo polymers in solution. Thus, the sol evolves towards the formation of a gel-like diphasic system containing both liquid and solid phases whose morphologies range from discrete particles to continuous polymer networks (Figure I.3.). Removal of the remaining liquid (solvent) phase requires a drying process, which is typically accompanied by a significant amount of shrinkage and densification. The rate at which the solvent can be removed is ultimately determined by the distribution of porosity in the gel. The ultimate microstructure of the final component will be strongly influenced by changes imposed upon the structural template during this phase of processing. Afterwards, a thermal treatment, or a firing process, is also necessary in order to favor further poly-condensation and to enhance the mechanical properties and structural stability via final sintering, densification, and grain growth. Sol-gel derived materials have diverse applications in optics, electronics, energy, space, bio-sensors, medicine (e.g., controlled drug release), and in reactive material and separation (e.g., chromatography) technology [92], [93]. Sol-gel technology has found increasing applications in the development of new materials for catalysis[94], [95], chemical sensors[96], [97], membranes[98], fibers[99], optical gain media[100], photochromic and non linear applications [101], [102], [103], and in solid state electrochemical devices [104]. The technology is utilized in a diverse range of scientific and engineering fields, such as the ceramic industry [93], nuclear field industry [93], and electronics industry [105]. The inherent advantages of the sol-gel process are summarized as follows [106]: better homogeneity and purity from raw materials; lower temperature of preparation;effective control of particle size, shape and properties; creation of special products as films and the possibility of designing the material structure and property through the proper selection of sol-gel precursor and other building blocks. Fundamental chemical reactions in the sol-gel process The hydrolysis and the polycondensation of titanium alkoxides proceed according to the following scheme [107]: (19) (20) (21)

Hydrolysis and condensation can be exothermic and violent, particularly in the case of transition metal alkoxides and usually they lead to undesirable routes. Therefore stabilizing agents can be added into the sols (acetic acid, ethyl acetoacetate), which prevent the process of precipitation by decreasing the rate of the hydrolysis and condensation reactions. In such case stable sols (colloidal solutions) are obtained. Condensation reactions can continue to build larger and larger metalcontaining molecules by the process of polymerization. When cross-linked polymers with an average size of several nanometers are formed, the sol is obtained. The final result of condensation/polymerization reactions is a gel, consisted of a three dimensional titania network that extends throughout the solution.

(22) Methods to obtain TiO2 sol-gel Titanium dioxide formed by sol-gel method with applications in wastewater photocatalytic processes, can be obtained, according to the literature [84], using various methods, various precursors, obtaining time and temperatures. Materials used in sol-gel methods: TTIP titanium tetraisopropoxide, TiCl4 titanium tetrachloride, CHD 1,4 cyclohexane diol, EtOH absolute ethanol, MeOH methanol, TEA tetraethylammonium, NH4OH ammonium hydroxide, C6H14 hexane. Fig. 1.4.1.2. Four methods to obtain titanium dioxide by sol-gel technique

A gel forms because of the condensation of hydrolyzed species into a three-dimensional polymeric network. Any factor that affects either or both of these reactions is likely to impact the properties of the gel. These factors, generally referred to as sol-gel parameters, includes

type of precursor, type of solvent, water content, acid or base content, precursor concentration, and temperature [108]. These parameters affect the structure of the initial gel and, in turn, the properties of the material at all subsequent processing steps. After gelation, the wet gel can be optionally aged in its mother liquor, or in another solvent, and washed. The time between the formation of a gel and its drying, known as aging, is also an important parameter. A gel is not static during aging but can continue to undergo hydrolysis and condensation[109]. Furthermore, syntesis, which is the expulsion of solvent due to gel shrinkage, and coarsening, which is the dissolution and reprecipitation of particles, can occur. These phenomena can affect both the chemical and structural properties of the gel after its initial formation. Then it must be dried to remove the solvent. Table 1.4.1.1. showed a summary of the key steps in a sol-gel process which includes the aim of each step along with experimental parameters that can be manipulated. Table 1.4.1.1.Important parameters in the various steps of sol-gel proces [110], [111], [112], [113]. Step Solution chemistry Aging Purpose To form gel To allow a gel to undergo changes in properties To remove solvent for a gel To change the physical / chemical properties of the solid Important Parameters
Type of precursor; Type of solvent;Water content; Precursor concentration; Temperature; pH Time; Temperature;

Drying

Calcinatio n

Composition of the pore liquid; Aging environment; Drying method (evaporative, supercritical, and freeze drying); Temperature and heating rate; Time Pressure and pressurization rate; Temperature Heating rate;Time; Gaseous environment (inert, reactive gases);

In most of the experiments concerning the TiO2 photocatalysis, the photocatalyst was used in the powder form and the recovery of powder was difficult to execute. Thus, immobilization of the TiO2 semiconductor particles is necessary for industrial applications. The methods used for synthesis of titanium oxide powder include alkali precipitation, thermal decomposition, hydrothermal synthesis, sol-gel [114], [115], [116] and other routes. Among all synthetic procedures, preparation of TiO2 by a solgel route remains one of the most attractive due to the possibility of preparing powders or thin films. For the preparation of thin films with solgel powder the dipping and doctor blade techniques could be used.

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