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Doped-TiO2: a review
ARTICLE in RECENT PATENTS ON ENGINEERING NOVEMBER 2008
DOI: 10.2174/187221208786306289
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Adriana Zaleska-Medynska
University of Gdansk
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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.
2.
3.
Adriana Zaleska
Doped-TiO2
Table 1.
Metal dopants
Kind of
dopant
159
Preparation method
Potential application
References
Ag
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.
Degradation of
nitrophenol in aqueous
phase
[22]
Fe
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.
Wastewater decoloring
[23]
Wastewater decoloring
[24]
Au
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.
Wastewater decoloring
[25]
Pt
Wastewater decoloring
[26]
Titanium nitride (TiN) oxidation : Heating of TiN at 450-550C for 2h in air (heating
and cooling temperature rate: 2C/min).
Photooxidation of
aromatic compounds
(e.g. toluene)
[27]
Treating anatase TiO2 powder ST01 in the NH 3 (67%)/Ar atmosphere at 600C for 3 h.
Photooxidation of
acetaldehyde in gas
phase
[18]
Wastewater decoloring
[28]
N, S
Photooxidation of
volatile compounds in
gas phase (e.g. acetone
and formaldehyde
[29]
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.
Wastewater decoloring
Photooxidation of
phenol compounds in
aqueous phase
[31]
Anatase TiO2 powder (ST01) was grinding with boric acid triethyl ester and calcinated
in air at 450C.
Photooxidation of
phenol compounds in
aqueous phase
[32]
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.
Photooxidation of
phenol compounds in
aqueous phase
[33]
Nonmetal dopants
Degradation of NOx;
[30]
Adriana Zaleska
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.
Doped-TiO2
161
Adriana Zaleska
Fig. (3). Gradient composition of TiO2 doped with nonmetal anions according to [56].
is
Doped-TiO2
using a pulsed microplasma cluster source, using the apparatus disclosed in US6392188.
163
[5]
[6]
[7]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
Adriana Zaleska
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
[55]
[56]
[57]
[58]
[59]
[60]
[61]