# Patent

## Title
Ultraviolet and visible-light-sensitive titania-based photocatalyst

## Abstract

The present invention provides photocatalysts showing excellent sensitivity not only in ultraviolet light region but also in visible light region. The ultraviolet and visible light-sensitive titania-based photocatalysts according to the present invention are characterized by their composition as expressed by a general formula: TiSixNyO2+2x−y (where 0.01<x<1 and 0.003<y<0.3). The invented photocatalysts have optical properties that the relative absorbance at 450 nm to that of 300 nm is not lower than 0.1 and the relative absorbance at 600 nm to that of 300 nm is not higher than 0.1.

## Background
FIELD OF THE INVENTION 
The present invention relates to titania photocatalysts which show excellent visible-light-sensitivity. 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. There are invented some significant advantages, in this invented material, of being safe, nontoxic, or inexpensive. With respect to the distinguished nature mentioned above, we can utilize this new material as coating substance of various equipments, appliances and utensils, which are used for glasses, mirrors, lightings, papers, or clothes, as well as construction materials.
DESCRIPTION OF THE RELATED ART
Titania (titanium oxide) is known as a semiconductor material which exhibits photocatalytic activity for decomposition of organic substances under ultraviolet (UV) light irradiation. A photocatalytic reaction generally includes the following processes: when photons have an energy higher than the semiconductor band gap, they are absorbed, and electrons in the valence band are promoted to the conduction band, leaving positive holes in the valence band. The excited electron is used to reduce substances, and the positive hole is used to oxidize substances on the surface of the catalyst. Now, photocatalytic reaction systems collect great attention because the systems necessitate only photons as the energy source, and the photoinduced chemical species have strong oxidation and reduction potential even at room temperature. Recently, in the field of chemical synthesis and decomposition of harmful organic substances in air or water, some systems came to be considered as practically useful processes.
A patent, WO96/29375, shows another property of titania photocatalysts, termed as ‘photoinduced superhydrophilic property.’ When a titania is coated on glasses and mirrors, the visibility degradation by droplets of water on them does not occur according to this property.
However, the band gap energy of titanias (anatase structure) is 3.2 eV, which corresponds to light in UV region (wave length<388 nm). Therefore, titanias show photocatalytic activity only by ultraviolet light irradiation. It is generally said that the solar light coming the earth's surface includes only about 3% of UV light. This means that a titania photocatalyst can use only about 3% of the solar energy.
To improve the optical property of the titania photocatalysts, several methods have been proposed, for examples, doping transition metals, such as chromium and iron, or nitrogen into titania photocatalysts. Disclosed patents, JP-H9-192496-A, WO01/010552 and JP-H15-200057-A, indicate that titania catalysts containing these elements have visible light sensitivity. They demonstrated that organic substances which may cause contamination and/or odor are decomposed by using indoor fluorescent lights. On the other hand, it is also known that the introduction of the alien elements to titanias promotes the recombination of electron and positive hole, and this resulted in the decrease in the efficiency of photocatalytic reactions. Although several types of visible-light-sensitive photocatalysts have been proposed hitherto, the mount of the doping elements are low in order to avoid the recombination of the electron-hole pairs, and consequently, the absorption efficiency for the light in visible region is not high. To improve the photocatalytic activity under visible light irradiation, a catalyst with a high absorption property at visible light region is strongly required.
SUMMARY OF THE INVENTION 
The present invention provides photocatalytic materials showing excellent photocatalytic activity not only under ultraviolet light irradiation but also under visible light irradiation.
The UV and visible-light-sensitive titania photocatalysts described in the present invention have characteristic compositions expressed by a general formula: TiSixNyO2+2x−y (where 0.01<x<1 and 0.003<y<0.3). The materials also have characteristic optical properties; the relative absorbance at 450 nm is not lower than 0.1, and the relative absorbance at 600 nm is not higher than 0.1. Here, the relative absorbances are defined as the following equations for 450 nm and 600 nm, respectively, based on the absorbance at 300 nm:

(Relative absorbance at 450 nm)=(Absorbance at 450 nm)/(Absorbance at 300 nm)

(Relative absorbance at 600 nm)=(Absorbance at 600 nm)/(Absorbance at 300 nm)

In FIG. 1, the structure of titania of anatase structure is illustrated. In a normal titania of anatase structure, Ti atoms are located in octahedral sites shown as small open circles in FIG. 1. 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 present 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 titanias.
We have found that the nitrogen-doped silica-modified titanias exhibit photocatalytic activities higher than conventional titania-based photocatalysts under visible light irradiation. Among the various nitrogen-doped silca-modified titanias, superior photocatalytic activities are obtained using the materials that have the composition expressed as a general formula of TiSixNyO2+2x−y where 0.03≦x≦0.3 and 0.005≦y≦0.03. These materials possess characteristic absorption spectra; the relative absorbance at 450 nm is not lower than 0.2, and the relative absorbance at 600 nm is not higher than 0.05.
The photocatalysts as mentioned above are prepared by introducing nitrogen to the silica-modified titanias by ammonia treatments at high temperatures. The values of x and y are properly adjusted by changing the ratio of the reactants used in the preparation of the silica-modified titania, and also by changing the conditions of the nitrogen doping, such as flow rate and concentration of the ammonia, heating temperature, and treatment period. Furthermore, the values of x and y are varied by heating the samples under oxidative atmosphere after the NH3 treatment.
The photocatalysts in this invention shows an excellent visible-light-sensitivity compared to conventional visible-light-sensitive photocatalysts. Therefore, a wider region of the light, ranging from ultraviolet to visible or abundantly included in sunlight, is efficiently utilized. The thus-obtained nitrogen-doped silica-modified titanias are provided for various applications, such as decontamination, self-cleaning, deodorant, disinfection and antibacterial materials. Because they absorb a wide range of light efficiently, they may be utilized even indoor where light intensity is relatively weak.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows structure of anatase.
FIG. 2 shows UV-Vis absorption spectra of (a) silica-modified titania XG(0.1) and (b) titania XG(0) treated in NH3 at high temperatures.
FIG. 3 shows XRD patterns of (a) silica-modified titania XG(0.1) and (b) titania XG(0) after the NH3 treatment.
FIG. 4 shows UV-Vis absorption spectra of silica-modified titania XG(0.1) treated in NH3 followed by calcination in air.
FIG. 5 shows emission spectrum of the blue LED used for the photocatalytic decomposition of RhB.
FIG. 6 shows photocatalytic decomposition of RhB under visible light irradiation using nitrogen-doped silica-modified titanias.
FIG. 7 shows photocatalytic decomposition of acetaldehyde under visible light irradiation using nitrogen-doped silica-modified titanias.
FIG. 8 shows 01s XPS spectra of the silica-modified titanias.
FIG. 9 shows unit cell volume of the silica-modified titanias.



DESCRIPTION OF THE PREFERRED EMBODIMENTS
(Synthesis of Silica-Modified Titanias and Introduction of Nitrogen in the Silica-Modified Titanias)
25 g of tetraisopropyl titanate, 1.83 g of tetraethyl orthosilicate and 100 ml of 1,4-butanediol were mixed together (atomic ratio of the charged Si/Ti=0.1) and set in an autoclave. After the system inside was replaced by nitrogen, the mixture was heated from room temperature to 300° C. at a rate of 2.3° C./min. and held at 300° C. for 2 hours. While keeping the temperature at 300° C., the valve of the autoclave was slightly opened and the vapor phase in the autoclave was removed off. After cooling, a xerogel product was obtained. The product was calcined at 500° C. for 30 minutes in air to give a silica-modified titania. The silica-modified titania obtained is designated as XG(0.1). Silica-modified titanias with different Si/Ti ratios are prepared by changing the amounts of the Si and Ti sources, and the products are designated as XG(x) where x is the charged ratio of Si/Ti.
Collection of the silica-modified titania after heating in the autoclave was carried out in another way; after the heating as same as mentioned above, the assembly was cooled down to room temperature, to give the solid product suspended in the solvent. The solid product was collected by centrifugation, washed with methanol, and air-dried. The obtained product was calcined at 500° C. for 30 minutes. The silica-modified titanias thus-prepared is designated as GT(x) where x is the charged ratio of Si/Ti. Titanias without silica-modification, XG(0) and GT(0), were also prepared in the same way as mentioned above.
The preparation method mentioned above is same as the method described in a patent, JP-H12-254493-A. However, by other preparation methods, silica-modified titanias having similar properties as mentioned hereafter are obtained.
The silica-modified titania thus-prepared was set in a tube and contacted to an ammonia gas flow at a rate of 100 mL/min. The sample was heated at 450 to 700° C. for 30 min or longer. A preferred time of the treatment is from 30 min to 1 hour because a prolonged time of the NH3-treatment results in the formation of TiN phase.
In FIG. 2, UV-Vis absorption spectra of the obtained photocatalysts are shown. FIG. 2(a) shows absorption spectra of the nitrogen-introduced silica-modified titania XG(0.1) and FIG. 2(b) shows those of XG(0). The temperature of the NH3-treatment and the surface composition of the samples are also shown in the figure. XG(0.1) or XG(0) without NH3-treatment exhibits an absorption only in the UV range (<400 nm). On the contrary, the NH3-treated samples, both XG(0.1) and XG(0), showed absorption at visible light region. As the treatment temperature was higher, the absorption at visible light region became stronger. The amount of the nitrogen doped (y in TiSixNyO2+2x−y) also increased as increasing the temperature. The XG(0.1) samples have stronger absorption at a wave length ranging from 400 to 500 nm compared with the XG(0) samples.
The compositions measured by X-ray photoelectron spectroscopy (XPS) and the relative absorbances at 450 nm and 600 nm are shown in Tables 1 and 2, for XG(0.1) and XG(0), respectively.







TABLE 1







The surface composition and optical property of XG(0.1)

















Relative
Relative
NH3 treating






Absorbance
Absorbance
temperature


Sample
Composition
x
y
at 450 nm
at 600 nm
(° C.)





XG(0.1)
TiSi0.1N0.002O2.198
0.1
0.002
0.050
0.010
450



TiSi0.1N0.005O2.195
0.1
0.005
0.205
0.011
500



TiSi0.1N0.014O2.186
0.1
0.014
0.360
0.025
550



TiSi0.1N0.044O2.156
0.1
0.044
0.666
0.130
600



TiSi0.1N0.064O2.136
0.1
0.064
0.697
0.263
650



TiSi0.1N0.101O2.099
0.1
0.101
0.856
0.817
700
















TABLE 2







The surface composition and optical property of XG(0)



















NH3






Relative
Relative
treating






Absor-
Absor-
tempera-






bance
bance
ture


Sample
Composition
x
y
at 450 nm
at 600 nm
(° C.)





XG(0)
TiN0.002O1.998
0
0.002
0.097
0.038
450



TiN0.007O1.993
0
0.007
0.228
0.081
500



TiN0.009O1.991
0
0.009
0.273
0.127
550



TiN0.017O1.983
0
0.017
0.406
0.247
600



TiN0.038O1.962
0
0.038
0.810
0.958
650



TiN0.184O1.816
0
0.184
0.839
0.950
700









FIG. 3. shows the XRD patterns of the silica-modified titania, XG(0.1), and titania, XG(0). Before the NH3 treatment, the samples show diffraction peaks corresponding to titania of anatase structure (2theta=25°, 37°, 48°, 54°, 55°, 63°, 69°, measured using CuKα radiation). After the NH3 treatment at 600° C., the samples preserved the anatase structure. However, when the NH3 treatment was carried out at 700° C. for 1 h, three diffraction peaks at 2theta=37°, 43°, 63° were detected. These peaks indicate the formation of TiN phase with a rock-salt structure. In the case of the silca-modified titania, XG(0.1), the peak intensities for the TiN phase were relatively weak than those of XG(0). These peaks became stronger as prolonging the treatment period.
Table 3 shows the composition and the relative absorbance of XG(0.1) treated in the NH3 flow and calcined in air for 30 minutes at 400° C.
As apparently seen in Table 3, the amount of nitrogen-doping was lowered by calcination in air after the NH3 treatment. FIG. 4 shows the UV-Vis absorption spectra of XG(0.1) after the NH3 treatment followed by calcination in air. Compared with the spectra before the calcination in air, FIG. 2(a), the absorption at visible light region decreased significantly. The absorption at higher wavelength (>500 nm) decreased significantly, whereas the absorption at 400–500 nm was preserved. By XRD the TiN phase diminished after the calcination in air.







TABLE 3







The surface composition and optical property of XG(0.1) after the NH3


treatment followed by calcination in air.

















Relative
Relative
NH3 treating






Absorbance
Absorbance
temperature


sample
Composition
x
y
at 450 nm
at 600 nm
(° C.)





XG(0.1)
TiSi0.1N0.002O2.198
0.1
0.002
0.102
0.004
500



TiSi0.1N0.010O2.190
0.1
0.010
0.202
0.013
550



TiSi0.1N0.014O2.186
0.1
0.014
0.407
0.027
600



TiSi0.1N0.022O2.178
0.1
0.022
0.581
0.048
650



TiSi0.1N0.025O2.175
0.1
0.025
0.662
0.076
700









[Evaluation of Photocatalytic Activities by Measuring the Decomposition of Rhodamine B]

Photocatalytic activities of the ammonia-treated silica-modified titanias were evaluated by measuring the decomposition rate of an organic dye, Rhodamine B (RhB). Tested catalysts are as follows; XG(0), XG(0.1), and XG(0.2) after the NH3 treatment at 600° C., and XG(0.1), XG(0.2), GT(0.1), and GT(0.2) treated in NH3 at 600° C. followed by calcination in air at 400° C. The catalyst (20 mg) was dispersed in 100 mL of 1.0×10−5 mol/L RhB. This suspension was irradiated using blue LEDs (Nichia Kagaku Co., Ltd., NSPB510S ) under magnetic stirring at room temperature. The emission spectrum of the blue LED is shown in FIG. 5.
After a certain period of irradiation, a portion of the suspension was taken and filtered to measure the absorbance of the RhB solution. The concentration of the remained RhB was determined from the absorbance at 554 nm. The results of the photocatalytic decomposition of RhB as the function of the irradiation time are shown in FIG. 6. Compared with the titania without silica-modification, XG(0), the nitrogen-doped silica-modified titanias, XG(0.1), XG(0.2), GT(0.1) and GT(0.2) exhibited higher photocatalytic activities.
[Evaluation of Photocatalytic Activities by Measuring the Decomposition of Acetaldehyde]
Decomposition of acetaldehyde was carried out in a sealed glass vessel. A portion of the catalyst (0.2 g) dispersed on a glass filter was placed in a closed glass vessel (1 L) and 0.2 mmol of acetaldehyde was injected into the vessel. After the sample was kept in the dark for 1 h, it was irradiated using a 300 W xenon light (Optical Modulex SX-UI300XQ, Ushio Inc.) through a UV cut-off filter (L-42, Asahi Technoglass Co. Ltd.) and an infrared cut-off filter (Super Cold Filter, Ushio Inc.). After a certain period of irradiation time, a small portion of the gas inside the vessel was taken to measure the CO2 generated using a gas chromatography (Shimadzu GC-8A).
The results of the photocatalytic decomposition of acetaldehyde are shown in FIG. 7. A commercially available titania (P-25) and XG(0) without the NH3 treatment showed no photocatalytic activities under visible light irradiation. Using the nitrogen-doped XG(0), equivalent to a conventional catalyst, about 8 μm of CO2 formation was observed after 5 hour of the irradiation time. On the contrary, the nitrogen-doped silica-modified titanias XG(x)s produced 16–40 μm of CO2, indicating these catalysts have 2–5 times higher photocatalytic activities than the nitrogen-doped titania photocatalyst without silica-modification.
[Characterizations of the Silica-Modified Titanias]
Table 4 shows the surface compositions of the nitrogen-doped silica-modified titanias measured by XPS.







TABLE 4







Surface composition of the nitrogen-doped silica-modified titanias after the NH3


treatment at 600° C. for 1 h, followed by calcination at 400 ° C. for 30 min.
















Si/Ti (charged)
0
0.02
0.06
0.1
0.2
0.3
0.4
0.5
1





O/Tia
2.323
2.415
2.560
2.759
3.194
3.424
4.137
5.044
30.043


N/Tia
0.005
0.008
0.013
0.014
0.025
0.022
0.021
0.026
 0.027


Si/Tia
—
0.056
0.127
0.187
0.397
0.472
0.734
1.167
11.287





aMeasured by XPS.













TABLE 5







Physical properties of the silica-modified titanias. 










Sample
BET surface
Crystallite
Bulk densityb


(Si/Ti charged ratio)
area (m2/g)
sizea (nm)
(g/cm3)













XG(0)
80
18
0.123


XG(0.02)
112
15
0.171


XG(0.1)
151
11
0.200


XG(0.2)
190
10





aXRD


bMercury porosimetry






Table 5 shows physical properties of the silica-modified titanias. As increasing the amount of the silica-modification, the BET surface area increased and the crystallite size decreased. When the amount of silica was excessively high, the photocatalytic activity was quite low. The reason for this is that the excess silica tends to coat the titania surface. The Si/Ti ratio, therefore, is preferred not to be higher than 1.
FIG. 8 shows O1s XPS spectra of XG(0.1) before the NH3 treatment. Two components are recognized at 532 eV and 530 eV, indicating at least two types of oxygen are present in the sample. The component at 530 eV is attributed to the oxygen in titania of anatase structure and the other one at 532 eV is to the oxygen concerning to the Si—O—Ti bond.
The relationship between the ratio Si/(Si+Ti) and the unit cell volume of the silica-modified titania is shown in FIG. 9. As increasing the Si/(Si+Ti), the unit cell parameter decreased, indicating the formation of silica-titania solid solution.

## Claims

1. An ultraviolet and visible-light-sensitive titania-based photocatalyst, which is expressed by a general formula: TiSixNyO2+2x−y (where 0.01<x<1 and 0.003<y<0.3), has a relative absorbance at 450 nm compared with that of 300 nm not lower than 0.1, and has a relative absorbance at 600 nm compared with that of 300 nm not higher than 0.1.

2. An ultraviolet and visible-light sensitive titania-based photocatalyst according to claim 1 which has a relative absorbance at 450 nm compared with that of 300 nm not lower than 0.2, and has a relative absorbance at 600 nm compared with that of 300 nm not higher than 0.05.

3. An ultraviolet and visible-light-sensitive titania-based photocatalyst according to claim 1 which has following composition as expressed in a general formula: TiSixNyO2+2x−y, 0.03≦x≦0.3 and 0.005≦y≦0.03.

4. A preparation method of an ultraviolet and visible-light-sensitive titania-based photocatalyst, whose preparation method is characterized in that silica-modified titanias, in which Si atoms are incorporated in the crystal structure of titania, are heated in ammonia atmosphere preferably at a temperature ranging from 450 to 700° C., and then heated in an oxidative atmosphere preferably at a temperature ranging from 300 to 600° C.