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Doped-TiO2: a review

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DOI: 10.2174/187221208786306289

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 Recent Patents on Engineering 2008, 2, 157-164 157

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, non-
metal 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 mechanism of heterogeneous photocatalysis in the presence

of TiO2 is also discussed.
Strong oxidation and reduction power of photoexcited
titanium dioxide (TiO2) was realized from the discovery of 1.1. Mechanism of Photoactivity of Pure TiO2 and TiO2
Honda-Fujishima effect. In 1972, Fujishima et al. [1] Doped with Metal and Nonmetal Species
reported photoinduced decomposition of water on TiO 2
The photocatalytic mechanism is initiated by the
electrodes. Since Frank and Bard [2] first examined the
possibilities of using TiO2 to decompose cyanide in water, absorption of the photon hv1 with energy equal to or greater
than the band gap of TiO2 (~3.3 eV for the anatase phase)
there has been an increasing interest in environmental
producing an electron-hole pair on the surface of TiO 2
applications. Photocatalytic reactions at the surface of
nanoparticle as schematized in Fig. (1). An electron is
titanium dioxide have been attracting much attention in view
promoted to the conduction band (CB) while a positive hole
of their practical applications to environmental cleaning such
is formed in the valence band (VB). Excited-state electrons
as self cleaning of tiles, glasses, and windows. Titanium
dioxide represents an effective photocatalyst for water and and holes can recombine and dissipate the input energy as
heat, get trapped in metastable surface states, or react with
air purification and for self-cleaning surfaces. Additionally,
electron donors and electron acceptors adsorbed on the
it can be used as antibacterial agent because of strong
semiconductor surface or within the surrounding electrical
oxidation activity and superhydrophilicity [3]. TiO2 shows
double layer of the charged particles. After reaction with
relatively high reactivity and chemical stability under
water, these holes can produce hydroxyl radicals with high
ultraviolet light (
<387nm), whose energy exceeds the band
gap of 3.3 eV in the anatase crystalline phase. The redox oxidizing potential. Depending upon the exact
conditions, the holes, OH radicals, O2-, H2O2 and O2 itself
development of photocatalysts exhibiting high reactivity
can play important roles in the photocatalytic reaction
under visible light (
> 400 nm) should allow the main part of
mechanism [16-17].
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; Fig. (1). Mechanism of TiO2 photocatalysis: hv1: pure TiO2; hv2 :
E-mail: azal@chem.pg.gda.pl metal-doped TiO2 and hv3: nonmetal-doped TiO2.

1872-2121/08 $100.00+.00 © 2008 Bentham Science Publishers Ltd.

158 Recent Patents on Engineering 2008, Vol. 2, No. 3
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 photo-
activity.
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.
2. 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.
3. 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.
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 (150-
200 keV) was applied, then calcined in oxygen at 450-
475°C. 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
Adriana Zaleska
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 230°C for 2h in
the presence of water. Resulting powders were rinsed, dried
and calcined at 560°C. 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 150°C, pulverized and calcined
at 400°C. In the second procedure, the solution of vanadium
chloride, ethanol and titanium dioxide was slowly dropped
into cooled acidic aqueous solution (0°C). Then, the solution
was dried at 110°C, 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 600°C 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 pow-
ders [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-
Doped-TiO2 Recent Patents on Engineering 2008, Vol. 2, No. 3 159

Table 1. Doping Moieties and Preparation Methods of Doped-Titanium Dioxide Photocatalysts

Kind of Doped
Preparation method Potential application References
dopant element

Silver nitrate was mixed with reduction agent (sodium citrate tribasic dihydrate) and the
Degradation of
reaction temperature was raised to 80°C with continuous stirring. Then TIP and HNO3
Ag nitrophenol in aqueous [22]
were added and the reaction was maintained at 50°C for 24 h. The prepared sol was
phase
dried at 105°C for 24 h and calcined at 300°C.

The reactive magnetron sputtering method: 99.99% titanium target and 99.9% iron
Fe pieces were placed in the reaction chamber and mixture of argon and oxygen was Wastewater decoloring [23]
introduced into the chamber during discharging.
Metal dopants

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
V Wastewater decoloring [24]
generated via the estrification of acetic and butanol. The suspension as dried at 150°C,
pulverized and calcined at 400°C for 0, 5 h.

Titanium (IV) butoxide dissolved in absolute ethanol was added to solution containing
Au tetrachloroauric acid (HAuCl4·4H2O), acetic acid and ethanol. The resulting suspension Wastewater decoloring [25]
was aged (2 days), dried under vacuum, grinding and calcinated at 650°C.

Photoreduction process: TiO2 was suspended in a mixture of hexachloroplatinic acid in

Pt methanol. The suspension was irradiated with a 125 W mercury lamp (60 min.). Pt-TiO2 Wastewater decoloring [26]
was separated by filtration, washed with distilled water and dried at 100°C for 24 h.

Photooxidation of
Titanium nitride (TiN) oxidation : Heating of TiN at 450-550°C for 2h in air (heating
aromatic compounds [27]
and cooling temperature rate: 2°C/min).
(e.g. toluene)
N
Photooxidation of
Treating anatase TiO2 powder ST01 in the NH 3 (67%)/Ar atmosphere at 600°C for 3 h. acetaldehyde in gas [18]
phase

S Oxidation annealing of titanium disulfide (TiS2) at 300-600°C. Wastewater decoloring [28]

Hydrolysis of Ti(SO4 )2 in NH3 aqueous solution. Precipitate was centrifuged, washed Photooxidation of
with distilled water and alcohol. Obtained gels were dried under vacuum at 80 for 10 h volatile compounds in
Nonmetal dopants

N, S [29]
and were ground to obtain xerogel. The xerogel was calcinated at 400-800°C in air for gas phase (e.g. acetone
3 h. and formaldehyde

Sol-gel method: TBOT was hydrolyzed in the presence of ethanol, water and nitric acid; Degradation of NOx;
[30]
precipitated titanium hydroxide was dried at 110°C and calcinated in air at 150-200°C. Wastewater decoloring
C
Acid-catalyzed sol-gel process. Alkoxidide precursor was dissolved in corresponding Photooxidation of
alcohol, mixed with hydrochloric acid aqueous solution. Obtained gel was aged for phenol compounds in [31]
several days and calcinated in air (3 h at 65°C and 3 h at 250°C) and grounded. aqueous phase

Photooxidation of
Anatase TiO2 powder (ST01) was grinding with boric acid triethyl ester and calcinated
B phenol compounds in [32]
in air at 450°C.
aqueous phase

Sol-gel method: TIP was hydrolyzed in the presence of isopropanol and water, After Photooxidation of
P hydrolysis phosphoric acid was added. Dispersion was stirred for 2h, centrifuged at phenol compounds in [33]
3500 rpm and dried at 100°C. Obtained powder was calcinated at 300°C. aqueous phase

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 110°C, pulverized to obtain
xerogel and calcinated in air at temperature from 200 to
600°C.
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
160 Recent Patents on Engineering 2008, Vol. 2, No. 3
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, chro-
mium, 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 300°C and
then calcining it at a higher temperature, for example at least
500 or 600°C.
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 50-90°C. 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 μm. Described method represents a low-cost and
simple process for doped-nanoparticles manufacturing.
Adriana Zaleska
Another invention is related to TiO2 doped with molyb-
denum (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 dielec-
tric 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 com-
pound, (b) is produced by atomisation using a two-com-
ponent nozzle, an aerosol generator, or ultrasound atomi-
sation, 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].
Doped-TiO2
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 crystal-
lizing 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 con-
taining 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
Recent Patents on Engineering 2008, Vol. 2, No. 3 161
“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 pain-
tings such as silica, alumina, fluororesin (polytetrafluoro-
ethylene). 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 Ti-
O-X and TiO2 films, but also by changing the gas compo-
sition 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 photoca-
talytic 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 inter-
mediate with homogeneously distributed atoms of phos-
phorous through the matter; and (2) calcining the amorphous,
solid intermediate at a temperature between 300 and 900°C.
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 par-
ticle by excess phosphorus. Low concentration of phos-
phorus are evenly distributed throughout the anatase crystal
lattice and accordingly will not impact absorption properties
of the material. At a certain phosphorus content, a mono-
molecular layer of titanium phosphate is formed on the
particle surface and this significantly increases the
adsorption of organic compounds and accelerated the photo-
degradation 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
162 Recent Patents on Engineering 2008, Vol. 2, No. 3
Fig. (3). Gradient composition of TiO2 doped with nonmetal anions according to [56].
insulated from the compounds and photoactivity
accordingly decreased [57].
The object of another patent in this area is to provide
ultraviolet and visible-light-sensitive titania based photo-
catalyst [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 sulfur-
doped 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 100°C, 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 500°C, most
preferably in the temperature range 200 to 500°C. The
catalytic activity has been observed to decrease above and
under this calcinations temperature range.
Adriana Zaleska
is 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 photo-
catalytic 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 60°C forming a 22% TiO2 solution. Ortho-
titanic 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 nanostruc-
tured 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 1100°C in the presence of a carbon
source. Nanostructured titanium dioxide is preferably
obtained by means of supersonic cluster beam deposition
Doped-TiO2
using a pulsed microplasma cluster source, using the appa-
ratus 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 photo-
catalyst 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 550°C 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 increa-
sing 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 com-
pounds 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) photo-
catalyst 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
Recent Patents on Engineering 2008, Vol. 2, No. 3 163
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 photo-
catalytic 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. None-
metal doping seems to be more promising than metal doped-
TiO2.
One of the major challenges for the scientific and
industrial community involved in photocatalytic research is
to increase the spectral sensitivity of TiO2-based photoca-
talysts 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.
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