View
148
Download
5
Category
Tags:
Preview:
Citation preview
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].
1. Legrini, O.; Oliveros, E.; Braun, A. M. Chem. Rev. 93 (1993) 671;2. Mills, A.; Davies, R. H.; Worsley, D. Chem. Soc. Rev. 12 (1993) 417;3. Roberts, D.; Malato, S. The Science of the Total Environment 291 (2002) 85;4. Ollis, D.F.; Pelizzetti, E.; Serpone, N. Photocatalysis: Fundamentals and applications;
Wiley: New York, 1989;
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.
1. Fundamentals
1.1 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, radio-
active, 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 eco-
system 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 Standard Cotton Synthetic WoolpH 5.5-9 8-12 7-9 3-1BOD,mg/l, 5 days 30-350 150-750 150-200 5000-8000COD,mg/l, day 250 200-2400 400-650 10000-20000TDS, mg/l 2100 2100-7700 1060-1080 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
17. J.M. Poyatos, M.M. Munios, M.C. Almecija, J.C. Torres, E. Hontoria, F. Osorio, Advanced
oxidation processes for wastewater treatment: State of the Art, Water Air Soil Pollut (2010)
205:187-204;18. C. N., Sivaramakrishnan, Colourage, LI, No. 9, 27-32, 2004;
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 OperationsPrimary Screening, Sedimentation, Equalization, Neutralisation
Mechanical Flocculation and Chemical coagulation
SecondaryAerated lagoon, Trickling filtration, Activated sludge processOxidation ditch and pond, Anaerobic digestion
Tertiary
Oxidation technique, Electrolytic precipitation and Foam fractionationMembrane technologies, Electrochemical processesIon exchange method, Photo- catalytic degradationAdsorption (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, non-
biodegradable 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].
1.2 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 ReferencesAdsorbtion (activated carbon, silica, fly ash) [22]Ion exchange [23]
Membrane FiltrationReverse Osmosis [24]Ultrafiltration [25]
Ozonation [26]
EvaporationMultiple effect evaporation [27]Direct contact evaporation [28]
Crystallization [29]Specific Treatments [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].
1.2.1. 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 Electrochemical oxidation potential (EOP), V
EOP relative to chlorine
Fluorine 3.06 2.25Hydroxyl radical 2.80 2.05Atomic oxygen 2.42 1.78Ozone 2.08 1.52Hydrogen peroxide 1.78 1.30Hypochlorite 1.49 1.10Chlorine 1.36 1.00Chlorine dioxide 1.27 0.93Oxygen molecular 1.23 0.90
AOPs used for the treatment of wastewater are based on:
Ozone (O3);
Hydrogen Peroxide (H2O2);
Ozone + Hydrogen Peroxide;
Fenton’s 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 H2O2 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.
Fenton’s 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 catalyst’s 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].
1.2.2. 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,
43. A. Salinaro, Fundamental of heterogenous photocatalysis, Quebec, Canada, 2001;
the term „photocatalysis”is still disputable among scentists [46]. Serpone and Emeline took an
effort to systematized the definitions and terminology related to the photocatalysis [47].
44. N.Serpone, E. Pelizzetti, Photocatalysis: fundamentals and applications, John Wiley and
Sons, Inc., New York, 2000; 5. Beydoun, D., Amal, R., Low, G., McEvoy, S., J. Nanopart. Res. 1 (1999) 439 ;6. Guettaı, N., Ait Amar, H., Desalination 185 (2005) 427 ;7. Wu, J.M., Zhang, T.W., J. Photochem. Photobiol., A 162 (2004) 171;8. Saquib, M., Muneer, M., Desalination 155 (2003) 255;9. Kontos, A.I., Arabatzis, I.M., Tsoukleris, D.S., Kontos, A.G., Bernard, M.C., Petrakis, D.E.,
Falaras, P., Catal. Today 101 (2005) 275;10. Coronado, J.M., Maira, A.J., Conesa, J.C., Yeung, K.L., Augugliaro, V., Soria, J.,
Langmuir 17 (2001) 5368;11. Arabatzis, I.M., Antonaraki, S., T. Stergiopoulos, A. Hiskia, E. Papaconstantinou, M.C.
Bernard, P. Falaras, J. Photochem. Photobiol., A 149 (2002) 237;
12. Lei Ge. Mingxia Xu, Haibo Fang, Fabrication, characterization and
photocatalytic activities of TiO2 thin films from autoclaved-sol, Thin Solid Films 515 (2007)
3414–3420;13. Leen, S.C., Lee, J.H., Oh, T.S., Kim, Y.H., Sol. Energy Mater. Sol. Cells 75 (2003) 481;14. Seifried, S., Winterer, M., Hahn, H., Chem. Vap. Deposition 6 (2000) 239;15. Okuya, M., Nakade, K., Kaneko, S., Sol. Energy Mater. Sol. Cells, 70 (2002) 425;16. Subrata Das,Textile effluent treatment – A solution to the environmental pollution, 2004;19. C. Draghici, V. Oros, J. Pretty, Waste management, Ed. Academiei Romane, Bucuresti,
2003;20. J.C. Edwards, investigation of color removal by chemical oxidation for three reactive
textile dyes and spent textile wastewater, Blackburg, Virginia, 2000;21. R.C. Meena, Ram Babu Pachwarya, Vijay Kumar Meena and Shakuntla Arya, Degradation
of Textile Dyes Ponceau-S and Sudan IV Using Recently Developed Photocatalyst,
Immobilized Resin Dowex-11, American Journal of Environmental Sciences 5 (3): 444-450,
2009, ISSN 1553-345X;
22. Maria Visa, Absorbant materials with controlled surface properties, based on solid wastes,
for advanced wastewater treatment, Ph.D Thesis, Brasov, 2008;23. Roberto Juan, Susana Hernández, José M. Andrés, Carmen Ruiz, Ion exchange uptake of
ammonium in wastewater from a sewage treatment plant by zeolitic materials from fly ash,
Journal of Hazardous Materials, Volume 161, Issues 2-3, Pages 781-786, 30 January 2009,;24. S.S. Madaeni, M.R. Eslamifard, Recycle unit wastewater treatment in petrochemical
complex using reverse osmosis process , Journal of Hazardous Materials, Volume 174, Issues
1-3, Pages 404-409,15 February 2010;25. Juan Arévalo, Gloria Garralón, Fidel Plaza, Begoña Moreno, Jorge Pérez, Miguel Ángel
Gómez ,Wastewater reuse after treatment by tertiary ultrafiltration and a membrane bioreactor
(MBR): a comparative study, Desalination, Volume 243, Issues 1-3, Pages 32-41 July 2009;26. Kadir Turhan, Zuhal Turgut, Decolorization of direct dye in textile wastewater by
ozonization in a semi-batch bubble column reactor, Desalination, Volume 242, Issues 1-3,
Pages 256-263, June 2009;27. G. Libralato, A. Volpi Ghirardini, F. Avezzù, Evaporation and air-stripping to assess and
reduce ethanolamines toxicity in oily wastewater, Journal of Hazardous Materials, Volume
153, Issue 3, Pages 928-936, 30 May 2008;28. Gautham Parthasarathy, Russell F. Dunn, Graphical strategies for design of evaporation
crystallization networks for environmental wastewater , Advances in Environmental
Research,Volume 8, Issue 2, Pages 247-265, January 2004; 29. Stephan Tait, William P. Clarke, Jurg Keller, Damien J. Batstone , Removal of sulfate from
high-strength wastewater by crystallisation Water Research, Volume 43, Issue 3,Pages 762-
772, February 2009;30. I. Oller, S. Malato, J.A. Sánchez-Pérez, Combination of Advanced Oxidation Processes
and biological treatments for wastewater decontamination—A review, Science of The Total
Environment, Available online 16 October 2010;
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:
31. P.R. Gogate and A.B. Pandit. “A review of imperative technologies for wastewater
treatment II: Hybrid methods”. Advances in Environmental Research, 8 (3-4): 553-597, 2004;32. P.R. Gogate and A.B. Pandit. “A review of imperative technologies for wastewater
treatment I: Oxidation technologies at ambient conditions”. Advances in Environmental
Research, 8 (3-4): 501-551, 2004;33. P. Paraskeva and E. Diamadopoulos. “Technologies for olive mill wastewater (OMW)
treatment: A review”. J. Chem. Technol. Biot., 81 (9):1475-1485, 2006;34. S. Esplugas, D.M. Bila, L.G.T. Krause, and M. Dezotti “Ozonation and advanced oxidation
technologies to remove endocrine disrupting chemicals (EDCs) and pharmaceuticals and
personal care products (PPCPs) in water effluents”. J. Hazard. Mater., 149 (3): 631-642, 2007;35. M.B. Johnson and M. Mehrvar. “Aqueous metronidazole degradation by UV/H2O2 process
in singleand multi-lamp tubular photoreactors: Kinetics and reactor design”. Ind. Eng. Chem.
Res., 47 (17): 6525- 6537, 2008;36 . H.K. Moo-Young. “Pulp and paper effluent management”. Water Environ. Res., 79 (10):
1733-1741, 2007;37. G. Crini. “Non-conventional low-cost adsorbents for dye removal: A review”. Bioresour.
Technol., 97 (9): 1061-1085, 2006;38. P.C. Vandevivere, R. Bianchi and W. Verstraete. “Treatment and reuse of wastewater from
the textile wet-processing industry: Review of emerging technologies”. J. Chem. Technol.
Biot., 72 (4): 289-302, 1998;39. T. Aye, W.A. Anderson, and M. Mehrvar. “Photocatalytic treatment of cibacron brilliant
yellow 3G-P (reactive yellow 2 textile dye)”. J. Environ. Sci. Heal. A, 38 (9): 1903-1914,
2003;40. T. Aye, M. Mehrvar, and W.A. Anderson. “Effects of photocatalysis on the
biodegradability of Cibacron Brilliant Yellow 3G-P (Reactive Yellow 2)”. J. Environ. Sci.
Heal. A, 39 (1): 113-126, 2004;
(2)
(3)
(4)
(5)
(6)
(7)
(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 (hʋ ≥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].
41. S. Renou, J.G. Givaudan, S. Poulain, F. Dirassouyan, and P. Moulin. “Landfill leachate
treatment: Review and opportunity”. J. Hazard. Mater., 150 (3): 468-493, 200842. A. Vogelpohl, S.M. Kim, Advanced oxidation processes (AOPs) in wastewater treatment,
J. Ind.Eng.Chem., Vol. 10, No.1.2002,33-40; 45. J.M. Herrmann, Heterogenous photocatalysis: fundamental and applications to the removal
of various types of aqueous pollutant, Catalysis Today, 115-129, 2000; 46. A. Mills, S. Le Hunte, An overview of semiconductor photocatalysis, Journal of
Photochemistry and Photobiology A: Chemistry, 108, 1999, 1-35;47. N. Serpone, A.V. Emeline, Suggested terms and definitions in photocatalysis and
radiocatalysis, International Journal of Photoenergy, 4, 2002, 91-233;48. J. Zhao, T. Wu, K. Wu,K. Oikawa, H.Hidaka, N. Serpone, Photoassisted degradation of
dye pollutants, Environ. Sci.Technol., 32, 2000, 2394-2400;
Intermediates
(9)
(10)
(11)
(12)
(13)
(14)
(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 EXAMPLESAlkanes isobutene, pentane, heptanes, cyclohexane, paraffinsAliphatic carboxylic acids formic,ethanoic, propanoic, oxalic, butyric, malic acidsAlkenes propene, cyclohexeneAromatics benzene, naphtalenePhenolic compounds Phenol, hydroquinone, catechol, methylcatechol, resorcinolHalophenols 2-,3-,4-chlorophenol, pentachlorophenol, 4- fluorophenol
Surfactants sodium dodecylsulphate, polyethylene glycol, sodium dodecylbenzene sulphonate, trimethyl phosphate,
Herbicides atrazine, prometron, propetryne, bentazonPesticides DDT, parathion, lindane, tetrachlorvinphos, phenitrothionDyes 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)
Intermediates
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 TiO2. 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:
51. H. Gerischer, A. Heller, The role of oxigen in photooxidation of organic molecules on
semiconductor particles, The Journal of Physical Chemistry, 95, 2000, 5261-5267; 52. G. Mills, M.R. Hoffman, Photocatalytic degradation of pentachlorophenol on titanium
dioxide particle:identification of intermediates and mechanism of reaction, Environ. Sci.
Technol., 27, 2001, 1681-1689;53. C. S. Turchi, D. F. Ollis, Photocatalytic degradation of organic water contaminants:
Mechanisms involving hydroxyl radical attack, Journal of Catalysis, 122, 1999, 178-192;54. R.B. Draper, M.A. Fox, Titanium dioxide photosensitized reactions studied by diffuse
reflectance flash photolysis in aqueous suspension of TiO2 powder, Langmuir, 6,2000, 178-
192; 55. M.R. Hoffman, S.T. Martin, W. Choi, D.W. Bahnemann, Environmental application of
seconductor photocatalysis, Chemival Reviews, 95, 1999, 69-96; 56. A.L. Linsebigler, G. Lu, J. T. Y. Jr, Photocatalysis on titanium dioxide surface:principles,
mechanisms and selected results, Chem Rev., 95, 1998, 735-758;57. H. D. Lasa, B. Serrano, M.Salaices, Photocatalytic reaction engineering, Springer, New
York, USA, 2004, p. 1-15; 49. G. Liu, T. Wu, J. Zhao, Irreversible degradation of alizarin red under visible light radiation
in air-equilibrated aqueous titanium dioxide dispertions, Environ. Sci. Technol., 2001, 2081-
2087;50. J. Yang, C. Chen, H. Ji, Mechanism of titanium dioxide- assisted photocatalytic
degradation of dyes under visible radiation, J, Phys. Chem.B,109, 2005, 21900-21907;
Langmuir –Hinshelwood mechanism – a reaction between the •OH radicals at the surface
of the catalyst and the adsorbed pollutant molecule (P)
(16)
Eley – Rideal mechanism – a reaction between the •OH at the catalyst’s surface and the
pollutant molecule in the solution
(17)
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].
1.3 . 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 300–388 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
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, self-
cleaning 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].
65. J. Winkler, Titanium dioxide, Vincentz, Hannover, 2003, p. 3037;58 . O. Carp, C.L. Huisman, A. Reller, Prog. Solid State Chem. 32 (2004) 33.59. I.K. Konstantinou, V.A. Sakkas, T.A. Albanis,Water Res. 36 (2002) 2733.60. J. Perkowski, S. Bzdon,A. Bulska,W.K. Jo´ z´wiak, Polish J.Environ. Stud. 15(2003)
457.61. A. Fujishima, T.N. Rao, D.A. Tryk, J. Photochem. Photobiol. C 1 (2000) 1;62. K. Rajeshwar, C.R. Chenthamarakshan, S. Goeringer, M. Djukic, Pure Appl. Chem. 73
(2001) 1849;63. W.A. Zeltner, D.T. Tompkin, Ashrae Transactions, vol. III, American Society of Heating
and Air-Conditioning Engineers Inc., 2005, part 2, p. 532;64. Z. Zhang, P.A. Maggard, J. Photochem. Photobiol. A 186 (2007) 8. 66. U. Diebold, The surface science of titanium dioxide, Surface Science Reports, 48, 2003,
53-229;
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.
Table 1.3.1. Selected application of titanium dioxide in respect to its photoelectrochemical
properties [67], [68].
PROPERTY CATEGORY APPLICATION
Photocatalytic water purification
Drinking waterRiver water, ground water, lakes and water storage tanks
Others Fish feeding tanks, drain age water and industrial wastewater
Photoelectrochemical water decomposition
Hydrogen production
Fuel for automobiles sector, fuel for solid oxide fuel cell, fuel for energetic sector, for pharmaceutical and food industry
Self-cleaning
Materials for residential and office buildings
Exterior tiles, kitchen and bathroom components, interior furnishing, plastic surfaces, aluminium siding, building stone and curtains, paper window blinds
Materials for roads
Tunnel hall, noise barrier, traffic signs and reflectors
Air cleaning
Indoor air cleaners
Room air cleaner, photocatalyst-equipped air conditioners and interior air cleaner for factories
Outdoor air purifiers
Concrete for highway, roadways and footpaths, tunnel walls, noise barriers and building walls
Self-sterilizing HospitalTiles to cover the floor and walls of operating rooms, silicone rubber for medical catheters and hospital garments and uniforms
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 Anatase Rutile Crystallographic structure Tetragonal Tetragonal Space group I41/amd P42/mmm
Lattice parameters [nm]a= 0.3784b= 0.9515
a= 0.4594c= 0.2959
Volume of the unit cell/molecule [10-3nm3] 34.172 31.216
69. M. Schiavello, Heterogenius photocatalysis, John Wiley& Sons Ltd, 1997, p. 33-34; 70. K. Zakrzewska, Titanium dioxide thin film for gas sensors and photonic application, AGH,
Krakow, 2003, p. 14;
Density [g/cm3], T=298K 3.894 4.270Band gap energy (Eg) [eV] 3.26 3.05Electron effective mass (m*) 1m0 20m0
Hall mobility of electron [cm2/Vs], T=298K 4 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
60–70% reduction in performance is reported in aqueous systems for immobilized TiO2 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].
1.4 . 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], sol–gel method [85], doctor blade
[86].
Table 1.4.1. Routes of syntesis of titanium oxide
Preparation methods
Precursors References
Hydrothermalmethod
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 40°C. 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
[87]
separate beaker and dropped slowly into the surfactant solution with vigorous stirring. After addition, the reaction was carried out at 55°C for 2 h without stirring. At first, there was no precipitation, but after several minutes, a light yellow powder was obtained.
Sol-gel synthesis
The TiO2 sol was synthesized by acid catalyzed sol–gel 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 C3H7OHTitanium tetra-isopropoxide was added gradually to the aqueous solution of HNO3 solution under continuous stirring for 1.5–2 h to produce a transparent sol containing 2g of TiO2
[88]
Chemical vapor
deposition
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 287°C to 362°C, and the processing pressure was kept at 1 Torr.
[89]
Spray pyrolysis
deposition
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 300–500 -C
[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].
I.4.1. 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.
The formation of a metal oxide involves connecting the metal centers with either oxo
(M–O–M) or hydroxo (M–OH–M) 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)
Fig. 1.4.1.1. Sol-Gel process
(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 metal–containing 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
71. D. Gumy, A.G. Rincon, R. Hajdu, C. Pulgarin, Solar Energy 80 (2006) 1376; 72. W.A. Zeltner, D.T. Tompkin, Ashrae Transactions, vol. III, American Society of
Heating and Air-Conditioning Engineers Inc., 2005, part 2, p. 532; 73. K. Kabra, R. Chaudhary, R.L. Sawhney, Indian Eng. Chem. Res. 43 (2004) 7683;74. S. Hunoh, J.S. Kim, J.S. Chung, E.J. Kim, Chem. Eng. Comm. 192 (2005) 327; 75. S.-Z. Chen, P.-Y. Zhang,W.-P. Zhu, L. Chen, S.-M. Xu, Appl. Surf. Sci. 252 (2006)
7532;76. T. Kemmitt, N.I. Al-Salim,M.Waterland, V.J. Kennedy, A.Markwitz, Curr. Appl.
Phys. 4 (2004) 189;77. L.C. Macedo, D.A.M. Zaia, G.J. Moore, H. de Santana, J. Photochem. Photobiol.
A 185 (2007) 86;78. H. Kim, S. Lee, Y. Han, J. Park, J. Mater. Sci. 40 (2005) 5295;79. Hongyong Xie, Luping Zhu, Lingling Wang, Shengwen Chen, Dandan Yang, Lijun Yang,
Guilan Gao, Hao Yuan, Photodegradation of benzene by titanium dioxide nanoparticles
prepared by flame CVD process, Journal of Particuology, Vol. 9, Issue 1, 2011, p. 75-79;80. Min Wook Pyun, Eui Jung Kim, Dae-Hwang Yoo, Sung Hong Hahn, Oblique angle
deposition of TiO2 thin films prepared by electron-beam evaporation Review Article, Applied
Surface Science, Volume 257, Issue 4, 1 December 2010, Pages 1149-1153; 81. J T Gudmundsson, Ionized physical vapor deposition (IPVD): Magnetron sputtering
discharges, Journal of Physics: Conference Series 100 (2008) 082002;82. Anca Duta, TiO2 thin layers with controlled morphology for ETA (extremely thin absorber)
solar cells, Journal of Thin Solid Films, Vol.511-512, 2006, p. 195-198;83. Andronic, L., Manolache, S., Duta A., TiO2 Thin Films Prepared by Spray Pyrolysis
Deposition (SPD) and Their Photocatalytic Activities, Journal of Optoelectronics and
Advanced Materials” 2007, vol. 9, Issue 5; 84. Rakul K. Keswani, Harshad Ghodke, Deepa Sarkar, Kartic C. Khilar, Raman S.Srinivasa,
Room temperature synthesis of titanium dioxide nanoparticles of different phases in water in
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.
oil microemulsion, Journal of Colloids and Surfaces A: Physicochemical and Engineering
Aspects, Vol. 369, Issue1-3, 2010, p. 75-81;85. Yassine Bessekhouad, Didier Robert, Jean Victor Weber, Synthesis of photocatalytic TiO2
nanoparticles: optimization of the preparation conditions, Journal of Photochemistry and
Photobiology A: Chemistry 157 (2003) 47–53; 86. Andronic L., Duta A., The influence TiO2 powder and film on the photodegradation of
methyl orange, Journal of Materials Chemistry and Physiscs, Vol. 112, Issue 3, 2008, p. 1078-
1082;87. D. Kim, S. Kwak, Applied Catalysis A: General 323 (2007) 110–118;88. A Bhattacharyya, S. Kawi, M.B. Ray, Photocatalytic degradation of orange II by TiO2
catalysts supported on adsorbents, Catalysis Today 98 (2004) 431–439;89. D. Byun, Y. Jin, B. Kim, J. Kee Lee, D. Park Journal of Hazardous Materials B73 (2000)
199–206;90. I. Oja, A. Mere, M. Krunks, R. Nisumaa, C.-H. Solterbeck, M. Es-Souni, Thin Solid Films
515 (2006) 674 – 677;91. M. A. Hamid, I. A. Rahman, Preparation of titanium dioxide thin films by sol-gel dip
coating method, Malaysian Journal of Chemistry, 2003, vol.5, no.1, p. 086-091;92. Klein, L.C. Sol-gel optical-materials. Annu. Rev. Mater. Sci. 2002, 23, p. 437–452;93. Klein, L.C.; Woodman, R.H. Porous silica by the sol-gel process. Porous Ceramic Mater.
2003,115, p. 109–124;94. Schubert, U. Catalysts made of organic-inorganic hybrid materials. New J. Chem. 2003,
18, p. 1049–1058;95. Blum, J. Rosenfeld, A. Gelman, F. Schumann, H. Avnir, D. Hydrogenation and
dehalogenation of aryl chlorides and fluorides by the sol-gel entrapped Rhc1(3),-Aliquat 336
ion pair catalyst. J. Mol. Catal. 2004, A146, p. 117–122;96. Banet, P. Cantau, C. Rivron, C. Tran-Thi, T.H. Nanoporous sponges and proven chemical
reactions for the trapping and sensing of halogenetated gaseous compounds. Actual. Chim.
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 Purpose Important ParametersSolution
chemistryTo form gel
Type of precursor; Type of solvent;Water content; Precursor concentration; Temperature; pH
2009, 331, p. 30–35;97. Lin, J. Brown, C.W. Sol-gel glass as a matrix for chemical and biochemical sensing. Trac-
Trend. Anal. Chem. 2005, 16, p. 200–211;98. Xomeritakis, G. Tsai, C.Y. Jiang, Y.B. Brinker, C.J. Tubular ceramic-supported sol-gel
silica-based membranes for flue gas carbon dioxide capture and sequestration. J. Membrane
Sci. 2009, 341, p. 30–36;99. Zeng, Z.R. Qiu, W.L. Yang, M. Wei, X. Huang, Z.F. Li, F. Solid-phase microextraction of
monocyclic aromatic amines using novel fibers coated with crown ether. J. Chromatogr. 2001,
A934, p. 51–57;100. Gvishi, R. Narang, U. Ruland, G. Kumar, D.N. Prasad, P.N. Novel, organically doped, sol-
gel-derived materials for photonics: Multiphasic nanostructured composite monoliths and
optical fibers. Appl. Organomet. Chem. 2007, 11, p. 107–127;101. Levy, D. Esquivias, L. Sol–gel processing of optical and electrooptical materials. Adv.
Mater.,2005, 7, p. 120–129;102. Dunn, B. Zink, J.I., Optical-properties of sol-gel glasses doped with organic-molecules,
Journal Mater.Chem. 2001, 1, p. 903–913;103. Levy, D. Recent applications of photochromic sol–gel materials. Mol. Crys. Liq. Crys. A
2007, 297, p. 31–39;104. Dunn, B.; Farrington, G.C.; Katz, B. Sol-gel approaches for solid electrolytes and
electrode materials. Solid State Ionics 2004, 70, p. 3–10;105. Dulay, M.T.; Quirino, J.P.; Bennett, B.D.; Zare, R.N. Bonded–phase photopolymerized
sol-gel monoliths for reversed phase capillary electrochromatography. J. Sep. Sci. 2002, 25, p.
3–9;106. MacKenzie, J.D. Sol-gel research – Achievements since 1981 and prospects for the
Future. J. Sol-Gel Sci. Techn. 2003, 26, p. 23–27;67. M. Radecka, M. Rekas, Effect of hight- temperature treatment on n-p transition in titania, J.
Am. Ceram. Soc., 85, 2002, 346-354;
Aging To allow a gel to undergo changes in properties
Time; Temperature; Composition of the pore liquid; Aging environment;
DryingTo remove solvent for a gel
Drying method (evaporative, supercritical, and freeze drying);
Temperature and heating rate; Time Pressure and pressurization rate;
CalcinationTo change the physical / chemical properties of the solid
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 sol–gel route remains one of the
most attractive due to the possibility of preparing powders or thin films. For the preparation
of thin films with sol–gel powder the dipping and doctor blade techniques could be used.
REFERENCES
68. A. Gorzkowska –Sobas, Modify materials of titanium dioxide, AGH, University of Science
and Technology, 2006, p. 17-18;107. O. Harizanov, A. Harizanova, Solar Energy Materials and Solar Cells, 63, 2000, p. 185-
195; 108. S. Sakthivel, H. Kisch, Angew. Chem. Int. Ed., 42, 2003, 4908;109. D. I. Sayago, P. Serrano, O. Bohme, A. Goldoni, G. Paolucci, E. Roman, J. A. Martin-
Gago, Phys. Rev. B, 64, 2001, 205402;110. S. C. Pillai, P. Periyat, R. George, D. E. McCormack, M. K. Seery, H. Hayden, J.
Colreavy, D. Corr, S. J. Hinder, J. Phys. Chem. C 111, 2007, 1605;111. Y. Cong, J. Zhang, F. Chen, M. Anpo, J. Phys. Chem. C 111, 2007, 6976; 112. D. Bersani, P. P. Lottici, X. Ding, Appl. Phys. Lett. 72, 1998, 73; 113. E. Gyorgy, A. P. D. PinoP. Serra, J. L. Morenza, Applied Surface Science 186, 2002, 130;114. Baorang L, Xiaohui W, Minyu Y, Longtu L, 2003, Mater Chem Phys 78:184–188;115. Almquist CB, Biswas P, 2002, J Catal 212:145–156; 116. Mills A, Hill G, Bhopal S, Parkin IP, O’Neill SA, 2003, J Pho-tochem Photobiol. A
160:185–194;
Recommended