Recent Patents on Engineering 2008, 2, 157-164

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Doped-TiO2: A Review
Adriana Zaleska*
Department of Chemical Technology, Gdansk University of Technology, 80-952-Gdansk, Poland
Received: May 28, 2008; Accepted: June 16, 2008; Revised: June 17, 2008

Abstract: Titanium dioxide represents an effective photocatalyst for water and air purification and for self-cleaning surfaces. Additionally, it can be used as antibacterial agent because of strong oxidation activity and superhydrophilicity. TiO2 shows relatively high reactivity and chemical stability under ultraviolet light ( <387nm), whose energy exceeds the band gap of 3.3 eV in the anatase crystalline phase. The development of photocatalysts exhibiting high reactivity under visible light (> 400 nm) should allow the main part of the solar spectrum, even under poor illumination of interior lighting, to be used. Visible light-activated TiO2 could be prepared by metal-ion implantation, reducing of TiO2, nonmetal doping or sensitizing of TiO2 with dyes. This paper reviews preparation methods of doped-TiO2 with metallic and nonmetallic species, including various types of dopants and doping methods currently available. The mechanism of heterogeneous photocatalysis in the presence of TiO2 is also discussed.

Keywords: Doped-TiO2, metal-doping, monmetal-doping, TiO2 preparation methods, heterogeneous photocatalysis. 1. INTRODUCTION Strong oxidation and reduction power of photoexcited titanium dioxide (TiO2) was realized from the discovery of Honda-Fujishima effect. In 1972, Fujishima et al. [1] reported photoinduced decomposition of water on TiO 2 electrodes. Since Frank and Bard [2] first examined the possibilities of using TiO2 to decompose cyanide in water, there has been an increasing interest in environmental applications. Photocatalytic reactions at the surface of titanium dioxide have been attracting much attention in view of their practical applications to environmental cleaning such as self cleaning of tiles, glasses, and windows. Titanium dioxide represents an effective photocatalyst for water and air purification and for self-cleaning surfaces. Additionally, it can be used as antibacterial agent because of strong oxidation activity and superhydrophilicity [3]. TiO2 shows relatively high reactivity and chemical stability under ultraviolet light (<387nm), whose energy exceeds the band gap of 3.3 eV in the anatase crystalline phase. The development of photocatalysts exhibiting high reactivity under visible light (> 400 nm) should allow the main part of the solar spectrum, even under poor illumination of interior lighting, to be used. Several approaches for TiO2 modification have been proposed: metal-ion implanted TiO2 (using transition metals: Cu, Co, Ni, Cr, Mn, Mo, Nb, V, Fe, Ru, Au, Ag, Pt) [4-6], reduced TiOx photocatalysts [7-8], non-metal doped-TiO2 (N, S, C, B, P, I, F) [9-11], composites of TiO2 with semiconductor having lower band gap energy (e.g. Cd-S particles [12], sensitizing of TiO2 with dyes (e.g. thionine) [13] and TiO2 doped with upconversion luminescence agent [14,15]. In this paper, the recent patents pertaining to the preparation methods of doped-TiO2 with metallic and nonmetallic species, including various types of dopants and doping methods currently available are presented. The
*Address correspondence to this author at the Department of Chemical Technology, Gdansk University of Technology, 80-952-Gdansk, Poland; Tel: (++48-58)-347-2437; Fax: (++48-58)-347-2065; E-mail: azal@chem.pg.gda.pl 1872-2121/08 $100.00+.00

mechanism of heterogeneous photocatalysis in the presence of TiO2 is also discussed. 1.1. Mechanism of Photoactivity of Pure TiO2 and TiO2 Doped with Metal and Nonmetal Species The photocatalytic mechanism is initiated by the absorption of the photon hv1 with energy equal to or greater than the band gap of TiO2 (~3.3 eV for the anatase phase) producing an electron-hole pair on the surface of TiO 2 nanoparticle as schematized in Fig. (1). An electron is promoted to the conduction band (CB) while a positive hole is formed in the valence band (VB). Excited-state electrons and holes can recombine and dissipate the input energy as heat, get trapped in metastable surface states, or react with electron donors and electron acceptors adsorbed on the semiconductor surface or within the surrounding electrical double layer of the charged particles. After reaction with water, these holes can produce hydroxyl radicals with high redox oxidizing potential. Depending upon the exact conditions, the holes, OH radicals, O2-, H2O2 and O2 itself can play important roles in the photocatalytic reaction mechanism [16-17].

Fig. (1). Mechanism of TiO2 photocatalysis: hv1: pure TiO2; hv2 : metal-doped TiO2 and hv3: nonmetal-doped TiO2.
2008 Bentham Science Publishers Ltd.

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The visible light photoactivity of metal-doped TiO2 can be explained by a new energy level produced in the band gap of TiO2 by the dispersion of metal nanoparticles in the TiO2 matrix. As shown in Fig. (1) electron can be excited from the defect state to the TiO2 conduction band by photon with energy equals hv2. Additional benefit of transition metal doping is the improved trapping of electrons to inhibit electron-hole recombination during irradiation. Decrease of charge carriers recombination results in enhanced photoactivity. There are three different main opinions regarding modification mechanism of TiO2 doped with nonmetals. (1) Band gap narrowing; (2) Impurity energy levels; and (3) Oxygen vacancies. 1. Band gap narrowing: Asashi, et al. [18] found N 2p state hybrids with O 2p states in anatase TiO2 doped with nitrogen because their energies are very close, and thus the band gap of N-TiO2 is narrowed and able to absorb visible light. Impurity energy level: Irie, et al. [19] stated that TiO2 oxygen sites substituted by nitrogen atom form isolated impurity energy levels above the valence band. Irradiation with UV light excites electrons in both the VB and the impurity energy levels, but illumination with visible light only excites electrons in the impurity energy level. Oxygen vacancies: Ihara, et al. [20] concluded that oxygen-deficient sites formed in the grain boundaries are important to emerge vis-activity and nitrogen doped in part of oxygen-deficient sites are important as a blocker for reoxidation.

to dope a series of transition metals, such as V, Cr, Ni, Mn and Fe [35]. The iron-doped-TiO2 was prepared by the hydrothermal method [36]. Titanium (IV) tetra-tert-butoxide and FeCl3 or FeCl2 dissolved in n-octanol was heated at 230C for 2h in the presence of water. Resulting powders were rinsed, dried and calcined at 560C. Photocatalyst doped with FeCl3 have better photoactivity for degradation of dye in aqueous solution under UV and visible light. It was found that the amount of doped iron ions plays a significant role in affecting its photocatalytic activity [36]. A series of vanadium-doped TiO2 photocatalysts were synthesized by two modified sol-gel methods by Wu et al. [24]. In the first method, vanadyl acetalacetonate dissolved in n-butanol was mixed with titanium butoxide dissolved in acetic acid. Hydrolysis was completed by the water generated via the estrification of acetic acid and butanol, then the solution was dried at 150C, pulverized and calcined at 400C. In the second procedure, the solution of vanadium chloride, ethanol and titanium dioxide was slowly dropped into cooled acidic aqueous solution (0C). Then, the solution was dried at 110C, pulverized and calcined. Obtained vanadium-doped TiO2 shows a red-shift in the UV-vis spectra and has higher activity in photodegradation of dyes under visible light than pure TiO2 [24]. First non-metal doped TiO2 was described in 1986 by Sato, et al. [37]. They obtained N-TiO2 powders from a commercial titanium hydroxide by calcination. The powders showed higher photocatalytic activity for oxidation of carbon monoxide and ethane than standard TiO2 in the visible region (434 nm). But at that time, this result did not attract attention. Only in 2001, Asashi, et al. reported the band-gap narrowing of titanium dioxide by nitrogen doping [18]. They prepared TiO2-xNx films by sputtering the TiO2 target in a N2(40%)/Ar gas mixture and by treating anatase powder (ST01, Ishihara Sangyo Kaisha, Japan) in the NH3(67%)/Ar atmosphere at 600C for 3 h. Soon after, successfully prepared and exhibiting higher photoactivity under visible light - N-doped TiO2 was followed by other nonmetal doped titania photocatalysts such as carbon [38] sulfur [39,40], boron [32, 41], phosphorus [33, 42], flour [43] and iodine [44]. Titanium dioxide modified with non-metal atoms was prepared by hydrolysis of titanium precursors in the presence of dopant, followed by calcination [29-30, 45], gas-phase thin film deposition method [46], oxidative annealing of TiN, TiS2 or TiC powders [27, 28, 47] and atmospheric pressure plasma-enhanced nanoparticles synthesis (APPENS) [48], see Table 1. Concluding, the sol-gel process is one of the versatile methods to prepare nano-size materials. This technique does not require complicated instruments and provides simple and easy means for preparing nano-size particles. The incorporation of an active dopant in the sol during the gelation stage allows the doping elements to have a direct interaction with support, therefore, the material possesses catalytic or photocatalytic properties. A typical preparation procedure by the sol-gel method of doped TiO2 is shown in Fig. (2). Titanium precursor, such as titanium isoprooxide (TIP), tetrabutyl orthotitanate (TBOT), titanium tetra-

2.

3.

The modification mechanism of anatase doped with nonmetals was also analyzed by Zhao et al. [21]. They investigated N-TiO2 and concluded that TiO2 doped with substitutional nitrogen has shallow acceptor states above the valence state. In contrast, TiO2 doped with interstitial nitrogen has isolated impurity states in the middle of the band gap. These impurity energy levels are mainly hybridized by N 2p states and O 2p states. 1.2. Doping Moieties and Preparation Methods To enhance the photocatalytic effect in the visible light region, many producing methods were proposed to dope (or incorporate) trace impurity in TiO2 including: ion-assisted sputtering, plasma, ion-implantation, chemical vapor deposition (CVD) and sol-gel. A comprehensive list of doped TiO2 and methods of its preparation are shown in Table 1 [22-33]. In 2000, Anpo presented second generation titanium oxide photocatalysts - visible light response TiO2 obtained by an advanced high-voltage metal ion-implantation method [34]. The electronic properties of TiO2 was modified by bombarding them with high energy metal ions. The metal ions (specifically Cr and V ions) were injected into the deep bulk of the TiO2 when high acceleration energy (150200 keV) was applied, then calcined in oxygen at 450475C. Obtained photocatalysts worked effectively in decomposition of NO into N2 and O2 under visible light ( > 450 nm) [34]. The same method was next successfully used

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Table 1.
Kind of dopant

Doping Moieties and Preparation Methods of Doped-Titanium Dioxide Photocatalysts

Doped element

Preparation method Silver nitrate was mixed with reduction agent (sodium citrate tribasic dihydrate) and the reaction temperature was raised to 80C with continuous stirring. Then TIP and HNO3 were added and the reaction was maintained at 50C for 24 h. The prepared sol was dried at 105C for 24 h and calcined at 300C. The reactive magnetron sputtering method: 99.99% titanium target and 99.9% iron pieces were placed in the reaction chamber and mixture of argon and oxygen was introduced into the chamber during discharging. Sol-gel method: Solution 1 (vanadyl acetylacetonate dissolved in n-butanol) was mixed with solution 2 (acetic acid in titanium butoxide) and hydrolyzed (24 h) by the water generated via the estrification of acetic and butanol. The suspension as dried at 150C, pulverized and calcined at 400C for 0, 5 h. Titanium (IV) butoxide dissolved in absolute ethanol was added to solution containing tetrachloroauric acid (HAuCl44H2O), acetic acid and ethanol. The resulting suspension was aged (2 days), dried under vacuum, grinding and calcinated at 650C. Photoreduction process: TiO2 was suspended in a mixture of hexachloroplatinic acid in methanol. The suspension was irradiated with a 125 W mercury lamp (60 min.). Pt-TiO2 was separated by filtration, washed with distilled water and dried at 100C for 24 h. Titanium nitride (TiN) oxidation : Heating of TiN at 450-550C for 2h in air (heating and cooling temperature rate: 2C/min).

Potential application

References

Ag

Degradation of nitrophenol in aqueous phase

[22]

Fe Metal dopants

Wastewater decoloring

[23]

Wastewater decoloring

[24]

Au

Wastewater decoloring

[25]

Pt

Wastewater decoloring

[26]

Photooxidation of aromatic compounds (e.g. toluene) Photooxidation of acetaldehyde in gas phase Wastewater decoloring Photooxidation of volatile compounds in gas phase (e.g. acetone and formaldehyde Degradation of NOx; Wastewater decoloring Photooxidation of phenol compounds in aqueous phase Photooxidation of phenol compounds in aqueous phase Photooxidation of phenol compounds in aqueous phase

[27]

N Treating anatase TiO2 powder ST01 in the NH 3 (67%)/Ar atmosphere at 600C for 3 h. Oxidation annealing of titanium disulfide (TiS2) at 300-600C. Hydrolysis of Ti(SO4 )2 in NH3 aqueous solution. Precipitate was centrifuged, washed with distilled water and alcohol. Obtained gels were dried under vacuum at 80 for 10 h and were ground to obtain xerogel. The xerogel was calcinated at 400-800C in air for 3 h. Sol-gel method: TBOT was hydrolyzed in the presence of ethanol, water and nitric acid; precipitated titanium hydroxide was dried at 110C and calcinated in air at 150-200C. C Acid-catalyzed sol-gel process. Alkoxidide precursor was dissolved in corresponding alcohol, mixed with hydrochloric acid aqueous solution. Obtained gel was aged for several days and calcinated in air (3 h at 65C and 3 h at 250C) and grounded. Anatase TiO2 powder (ST01) was grinding with boric acid triethyl ester and calcinated in air at 450C. Sol-gel method: TIP was hydrolyzed in the presence of isopropanol and water, After hydrolysis phosphoric acid was added. Dispersion was stirred for 2h, centrifuged at 3500 rpm and dried at 100C. Obtained powder was calcinated at 300C. [18]

[28]

Nonmetal dopants

N, S

[29]

[30]

[31]

[32]

[33]

chloride, is mixed with dopant precursor dissolved in alcohol, followed by hydrolysis performed at the room or elevated temperature. The precipitate is dried usually at temperature range from 80 to 110C, pulverized to obtain xerogel and calcinated in air at temperature from 200 to 600C.

The following section reviews some of the latest patents in titanium dioxide doping by metallic and nonmetallic species. 2. RELATED PATENTS OF METAL-DOPED TIO2 Oxonica Ltd. is a developer of innovative surface-doped particles of TiO2 and ZnO [49]. This invention relates to

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Another invention is related to TiO2 doped with molybdenum (Mo) [51]. TiO-Mo monocrystalline substance could be obtained by mixing TiO2 with MoO3 in the specific proportion, pressure molding the mixture and calcining this in air. The above-mentioned molded body of TiO2 doped with Mo consists of polycrystalline substance well-regulated in crystal size. In case of the proportion of Mo doped in single crystal is less than 2.0 mol%, the granular growth of crystal is not caused but it is made dense and intercrystalline cracking is not caused. In case the proportion of Mo is more than 8.0 mol%, the granular growth of crystal is irregularly caused and the intercrystalline cracking is not caused. US6884739 is related to lanthanide-doped TiOx dielectric films obtained by plasma oxidation [52]. A method of forming a dielectric film includes evaporating a Ti source at a first rate to deposit a Ti on a substrate, evaporating a lanthanide source at a second rate to form a lanthanide doped Ti film, and oxidize the Ti/lanthanide film to grow a dielectric film on a substrate. The Ti and the lanthanide are evaporated using electron beam evaporation or are assisted by ion beam bombardment of the substrate surface during deposition. The evaporation of the Ti and lanthanide is followed by oxidation using a Kr/oxygen plasma. The next invention provides pyrogenically prepared titanium dioxide doped by an aerosol and containing, as a doping component, an oxide selected from the group consisting of zinc oxide, platinum oxide, magnesium oxide and/or aluminum oxide as the doping components [53]. Invented photocatalyst has either: a) a BET surface area of 65 m2/g to 80 m2/g and a doping component concentration of 40 ppm to 800 ppm, or b) a BET surface area of 35 m2/g to 60 m2/g and a doping component concentration of more than 1000 ppm. Process for preparation of doped-TiO2 comprising two main steps: (1) feeding an aerosol into a flame used for the preparation of pyrogenic titanium dioxide, and (2) separating the resulting photocatalys from the gas mixture; wherein the titanium dioxide is prepared by flame oxidation or flame hydrolysis, and wherein the aerosol: (a) comprises a salt solution or suspension containing: a metal salt, a metalloid salt, mixtures of a metal salt and a metalloid salt, a suspension of a metal insoluble in water, a suspension of a metalloid compound, or a mixture of a suspension of a metal insoluble in water and a suspension of a metalloid compound, (b) is produced by atomisation using a two-component nozzle, an aerosol generator, or ultrasound atomisation, and (c) is mixed homogeneously with a gas mixture, wherein the gas mixture further comprises air, and allowed to react in the flame. The core element of the apparatus is the open burner of known type, as is customarily used for the preparation of pyrogenic oxides. The burner consists of an inner nozzle, from which the main gas stream flows into the flame tube and burns. The inner nozzle is surrounded by a further nozzle (jacket nozzle), from which ring or secondary hydrogen flows in order to avoid caking. Between the nozzle outlet and the flame tube there is arranged a diaphragm through which the aerosol is fed in, the aerosol gas stream from the diaphragm being mixed homogeneously with the gas stream of the inner nozzle and the jacket nozzle [53].

Fig. (2). Typical procedure of doped-TiO2 preparation by sol-gel method.

metal-doped nanoparticles, which find utility as stabilizing ingredients within cosmetics to prevent degradation from sun light, for use in agriculture, horticulture and veterinary medicine, as coatings for plastics and for environmental protection. A particles of TiO2 or ZnO were doped with one or more other elements such as concentration of dopant in the surface of the particle is greater than that at the core of the particles. Suitable dopants for the oxide particles include manganese (especially in form of Mn3+), vanadium, chromium, cerium, selenium, iron, nickel, copper, tin, aluminum, lead, silver, zirconium, zinc and cobalt. The surface-doped particles of the present invention can be obtained by combining particles of a host lattice (TiO2) with a second component in the form of a salt in solution in water, and then baking it, typically at a temperature of at least 300C and then calcining it at a higher temperature, for example at least 500 or 600C. Patent application, published in 2006, is related to a method for preparing TiO2 /SiO2 aerogel micro-ball doped with iron [50]. Iron-doped TiO2 could be obtained by mixing TiOSO4 and FeCl3 with deionized water and adjusting pH value to 7-8. Obtained precipitate is washed and mixed with nitric acid solution at 50-90C. Subsequently, silica sol is prepared by mixing of silicasol with nitric acid and anhydrate ethyl alcohol. Then, titanium sol is mixed with SiO2 alcohol sol at 1:3-8 volume ratio. TiO2 /SiO2 composite sol is added into oil phase to obtain micro ball, washed with acetone and dries. Obtained micro-balls have diameter from 10 to 200 m. Described method represents a low-cost and simple process for doped-nanoparticles manufacturing.

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The titanium dioxides according to the invention may be used for the degradation of impurities in waste water and/or waste air and/or waste gases and for the sterilization of water with UV irradiation. In that case, the titanium dioxides may be used both suspended in the waste water and/or waste air and fixed to a support [53]. Japanese patent application describes method for crystallizing metal-doped TiO2 thin film and laminate having metal-doped TiO2 thin film [54]. In this method, a polymer film is subjected to a plasma treatment by applying high frequency electric power between two electrodes in an argon gas atmosphere, thereby the metal-doped TiO2 thin film highly crystallized and with enhanced electroconductivity is obtained. Another invention refers to metallic ion-doped nano TiO2 transparent photocatalytic emulsion and preparation method thereof [55]. According to the invention optical transparent lotion features in 0.5 to 10% TiO2 mixed with V, Sn, Zn, Fe, 1 to 10% emulsifier with the rest being water. It is obtained by making of titanic chloride water solution containing metal ions is hydrolyzed to generate TiO2, VO3 and Sn4+, Zn2+, Fe3+ or Ce3+ compound oxidation deposit. This method uses cheap titanium tetrachloride and ammonium vanadate, iron trichloride, tin tetrachloride and zinc sulfate, using low temperature complex hydrolysis to allow higher ability to mix and expanding spectral response zone to visible light. Photocatalytic emulsion could be used to degradation of organic pollutants utilizing sun light or irradiation emitted by fluorescent lamps [55]. 2. RELATED PATENTS OF NONMETAL-DOPED TIO2 Kabushiki Kaisha Toyota Chuo Kenkyusho is a developer of a photocatalytic material, a titanium compound Ti-O-X, exhibiting a photocatalytic action when exposed to light with a wavelength in the region of ultraviolet and visible irradiation [56]. Anion X is an element selected from B, C, P, S, Cl, As, Se, Br, Sb, Te, or I, or a molecule containing at least one of these elements. Materials are prepared by at least one of a method comprising substituting anions X for some the oxygen sites of titanium oxide crystals, a method comprising doping anions X between lattices of a titanium crystal and a method comprising doping grain boundaries of titanium oxide, or a combination of these methods. The photocatalytic materials, described in this invention, acquired a new energy level formed in a band gap of titanium oxide, which results in its increased photocatalytic activity by absorbing visible light. Thus, the photocatalyst can exhibit satisfactory photocatalytic activity even under solar or fluorescent light. Those material could be manufactured by the sol-gel method, chemical reaction method, treatment in plasma containing anion species X, ion implantation and RF magnetron sputtering. In the last method, substrate and titanium oxide target are set in the vacuum chamber of a RF magnetron sputtering device. Then, an appropriate amount of gas containing anions X (for example SO2 +O2) and an inert gas (for example Ar) are introduced into the vacuum chamber to conduct sputtering. Ti-O-X film is deposited on

substrate surface serving as support. Various materials such as SiO2 or ceramic were proposed for the support [56]. Furthermore, Ti-O-X can be applied not only in a thin film but can also be included in binding materials for paintings such as silica, alumina, fluororesin (polytetrafluoroethylene). Fig. 3 (a) shows the Ti-O-X film /2/ formed on the SiO2 substrate /1/ and film TiO2 /3/ formed thereon. That is, TiO2/Ti-O-X film of gradient composition is formed in which the density of X atoms is diminishes closer to the surface, and in which TiO2 is exposed at the outmost surface. It is suitable that the TiO2/Ti-O-X photocatalyst of gradient composition be in the form of grains having Ti-O-X part /4/ on the inside and TiO2 part /5/ on the surface, as shown in Fig. 3 (b). The gradient composition can be produced not only by heat treatment after lamination layer formation of TiO-X and TiO2 films, but also by changing the gas composition in an atmosphere according to the deposition state of the film [56]. The inventors suggested, that nonmetal-doping could improve the long-term hydrophilicity compared to that of the TiO2 film. TiO2/Ti-O-X film deposited on various surfaces could served as defogging agent and proofing against the effects of organic substance decomposition. The US Patent No. 2008045410 pertains to doped anatase-TiO2 composition that exhibits enhanced photocatalytic activity [57]. From the composition point of view, this invention provides a nanosized, crystalline titanium dioxide (anatase) composition. The composition is doped with phosphorus, and the doping level is between 0.10 and 0.55 weight percent. Providing method includes: (1) spray drying of a phosphorus-doped solution of titanium oxychloride, titanium oxysulphate or aqueous solution of another titanium salt to produce an amorphous titanium dioxide solid intermediate with homogeneously distributed atoms of phosphorous through the matter; and (2) calcining the amorphous, solid intermediate at a temperature between 300 and 900C. Phosphoric acid could be used a phosphorus precursor. The optimal doping level is 0.33 weight percent. The photocatalytic activity of the phosphorus-doped material is at least 100 percent greater than the undoped material [57]. Phosphorus has a limited solubility in the anatase lattice. In a calcination step, excess phosphorus is driven out from the lattice and ends up on the particle surface. Depending on the calcination temperature, titanium phosphate, titanyl phosphate, titanium pyrophosphate or their mixtures form on the particles surface. The enhanced photodegradation activity is explained by creation a thin layer on the nanoanatase particle by excess phosphorus. Low concentration of phosphorus are evenly distributed throughout the anatase crystal lattice and accordingly will not impact absorption properties of the material. At a certain phosphorus content, a monomolecular layer of titanium phosphate is formed on the particle surface and this significantly increases the adsorption of organic compounds and accelerated the photodegradation efficiency. Further, increasing phosphorus concentration induces the formation of a compact, thicker layer of titanium phosphate or pyrophosphate. The adsorption of organic compounds on the particle surfaces is concomitantly increased, but the photoactive TiO2 core is

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Fig. (3). Gradient composition of TiO2 doped with nonmetal anions according to [56].

insulated from the compounds and photoactivity accordingly decreased [57].

is

The object of another patent in this area is to provide ultraviolet and visible-light-sensitive titania based photocatalyst [58]. The photocatalysts, according to this invention, are characterized by their composition as expressed by a general formula: TiSixNyO(2+2x-y) (where 0.01<x<1 and 0.003<y<0.3). The invented photocatalysts have optical properties that the relative absorbance at region from 300 nm to 450 nm is not lower than 0.1. In a regular titania of anatase structure, Ti atoms are located in octahedral sites. When a titania is modified with silica, the thermal stability of the material is improved significantly. In a silica-modified titania, Si atoms are inserted to the tetrahedral holes of the anatase structure or Si atoms substitutes Ti atoms located in the octahedral sites in the crystal structure. In the presented invention, nitrogen atoms are introduced into the structure by NH3 treatments at high temperatures. The thus-obtained materials are described as nitrogen-doped silica-modified titania. The catalytic materials obtained in this invention can be widely used for various practical fields, such as air-cleaning, water-purification, self-cleaning, anti-fogging, disinfection, chemical synthesis, and hydrogen production via water decomposition. According to inventors, this material is safe, nontoxic and inexpensive. It could be utilized also as coating substance of various equipments, appliances and utensils, which are used for glasses, mirrors, lightings, papers, or clothes, as well as construction materials [58]. Another invention in this category, presents a sulfurdoped TiO2 having enhanced activity in the presence of visible light, the production method and use of the same [59]. A sulfur-containing titanium dioxide hydrate precipitate is obtained from an acid titanium oxysulphate solution at a temperature below the boiling point of the solution, e.g. in the range from 70 to 100C, using crystal nuclei and without addition of base. The precipitate is separated, washed and calcinated. Calcination of the hydrate precipitate is conducted in the temperature range 100 to 500C, most preferably in the temperature range 200 to 500C. The catalytic activity has been observed to decrease above and under this calcinations temperature range.

The photocatalytic titanium dioxide thus obtained has a specific area in the range from 100 to 250 m2/g and a 0.3 to 5% sulfur concentration. The calcinated end product is stable, and it has been stated to have an excellent photocatalytic effect at visible light wavelengths in different reactions. Higher photocatalytic activity has been confirmed in acetaldehyde decomposition and in anionic (SNC-)2 radical formation. The sulfur built in the product in accordance with the invention is based on precipitation from the sulfate solution conducted in acid conditions. Besides the presence of sulfur, the observed high catalytic activity may relate to the precipitation of titanium as orthotitanic acid. The precipitate has been confirmed to dissolve into 43% sulphuric acid at a temperature of 60C forming a 22% TiO2 solution. Orthotitanic acid produces a large specific area in the product, which is favorable in terms of photocatalytic activity. According to inventors, S-TiO2 could be used as a photocatalyst operating at visible light in the decomposition of organic compounds or microorganisms and in cleaning of aquarium water containing algae [59]. The next invention deals with a carbon-doped nanostructured TiO2 material having the following characteristics: an optical band gap lower than 2.1 eV and an optical transmittance below 90%, 50% and 10% for wavelengths lower than 650 nm, 500 nm, and 400 nm, respectively [60]. The C-TiO2 can be obtained by thermal assembling of TiO2 nanoparticles in the presence of a carbon source, which is preferably a carbon-containing atmosphere such as the air. It was observed that under thermal annealing the grain growth is modest, the nanostructure is retained and the rapid diffusion of C atoms present as contaminants in the atmosphere into titania nanocrystalline lattice is highly favored. A process for preparing a carbon-doped nanostructured TiO2 material comprises: a) providing TiO2 nanoparticles having average diameter below 10 nm assembled in a porous structure with density in the range from 2.4 to 2.8 g/cm3 ; b) thermally treating the nanostructured TiO2 at temperatures ranging from 900 to 1100C in the presence of a carbon source. Nanostructured titanium dioxide is preferably obtained by means of supersonic cluster beam deposition

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using a pulsed microplasma cluster source, using the apparatus disclosed in US6392188. The carbon-doped nanostructured TiO2 material could be utilized as photocatalysts, in solar energy conversion devices and gas sensors. The last invention in this section relates to titanium oxide-based photocatalysts which are activated in the visible light and o self-cleaning materials that are prepared by substituting O of pure TiO2 with C and N [61]. The photocatalyst has a general formula of TiO2-x-CxN wherein 0 < x+ < 0.22, 0 < x < 0.2, and 0 < < 0.02. A preparation method comprising a formation process of thin films by using Ti and inert gas, N2 and CO as mixed gas by reactive sputtering, and heat treating process of the formed thin film at a temperature between 450 and 550C for 2 to 4 hours, thereby crystallizing. The titanium oxide-based photocatalysts having a general formula of TiO2-x-CxN and self-cleaning materials according to this invention have a smaller optical band gap compared to pure titanium oxides, and therefore, the photocatalysts can be activated under the visible light range. In addition, they comprise only pure anatase crystallization phase, and since the crystallized particles are small in size, the efficiency and self-cleaning effect of the photocatalysts is very high [61]. 4. CURRENT & FUTURE DEVELOPMENTS The number of new publications, including patents, has been growing exponentially for the last decade. The increasing number of papers, reports, conference proceedings and patents results primarily from commercial interest in applications being developed in Japan in the early 70-ties. The photocatalytic oxidation of organic compounds in aqueous environment has received the most attention, but there is a rapidly increasing focus on the oxidation of volatile organic or inorganic compounds in the gas phase, including NOx and SOx. Photocatalytic reduction of organic compounds and metal-containing ions and studies on cell killing and disinfection by illuminated titanium dioxide have also received increasing attention. Consequently, primarily in Japan, but also in the United States and latterly in China, commercialization of TiO2 photocatalysis has been initiated in various fields. In Japan, the commercialization of TiO2-based photocatalytic products commenced in the mid-1990s. More than 2000 companies have joined in this new industry, whose products including: exterior construction materials (e.g. self-cleaning tiles, glass and tents), interior furnishing materials (e.g. self-cleaning and antibacterial tiles, wallpapers and window blinds), road construction materials (e.g. self-cleaning and air-cleaning tunnel walls, soundproof walls and lamp covers), purification facilities (e.g. air cleaners, air conditioners, purification system for wastewater and sewage, purification system for pools) and household goods (e.g. self-cleaning and antibacterial fibers, clothes and sprays). Presently, visible light-type TiO2 (MPT-621) photocatalyst based on the metal doping method, have been commercially available in the form of powders and colloidal solutions in Japan. The visible light photocatalyst MPT-621

is produced by treating platinum compound onto photocatalytic titanium dioxide which can be sensitized by visible light. MPT-621 potentially will be used for indoor antibacterial and self-cleaning applications and water cleanup with solar light. The current problem with doped TiO2 may be the loss of photoactivity during recycling and long-term storage. It was assumed, that the efficiency of metal doped-TiO2 under visible light strongly depended on the preparation method used. In same cases, such doped photocatalysts showed no activity under visible light and/or lower activity in the UV spectral range compared to the non-doped TiO2 because of high carrier recombination rates through the metal ion levels. The main present problem with nonmetal-doped TiO2 photocatalyst is that the photocatalytic activity under visible light is much lower than that under ultraviolet light. Therefore, development of new and optimization of existing photocatalyts exhibiting activity upon visible light with surface characteristics of improved performance and of the high chemical and physical stability are crucial for broader scale utilization of photocatalytic systems in commercial application. Such materials together with the development of technically applicable self aligning photocatalytic coating systems adaptable to the major substrates (polymers, glass, ceramics or metals) will represent a ground breaking step change in this field particularly in the economic viability of a range of potential processes. Nonemetal doping seems to be more promising than metal dopedTiO2. One of the major challenges for the scientific and industrial community involved in photocatalytic research is to increase the spectral sensitivity of TiO2-based photocatalysts to visible light. A major area of future research would be the development of new dopants, new method of dopant incorporation into TiO2 structure as well as new application for environmental technology. Future patents would deal with visible light-activated TiO2 functioning in the presence of solar irradiation. The most important challenge which faces titania-based catalysis is stable TiO2 with predictable photoactivity in UV and visible light. REFERENCES
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