CN105363427A - TiO2 nanomaterial with visible-light catalytic activity, and application and preparation method thereof - Google Patents
TiO2 nanomaterial with visible-light catalytic activity, and application and preparation method thereof Download PDFInfo
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- CN105363427A CN105363427A CN201510865890.7A CN201510865890A CN105363427A CN 105363427 A CN105363427 A CN 105363427A CN 201510865890 A CN201510865890 A CN 201510865890A CN 105363427 A CN105363427 A CN 105363427A
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Abstract
The invention discloses a nanomaterial with visible-light photocatalytic activity, and an application and a preparation method thereof, and particularly relates to a TiO2 nanomaterial with visible-light photocatalytic activity, and an application and a preparation method thereof. According to the TiO2 nanomaterial with visible-light photocatalytic activity, the particles of the nanomaterial are spherical and each has a diameter of 20-500 nm; and the surfaces of the particles are covered with Ti3+ and Ti-OH. The TiO2 nanomaterial disclosed by the invention can have a high light absorption property under the radiation of visible light, and meanwhile, the preparation technology of the TiO2 nanomaterial is simple. Only TiO2 and deionized water are used as raw materials, and no other reagents are used. Moreover, reaction devices for high temperature and high pressure are not needed. Therefore, the equipment is simple; the operation is convenient; the required time is short; and the process cost is reduced to a greater extent.
Description
Technical field
The present invention relates to a kind of nano material of visible light catalysis activity, application and preparation method thereof, be specifically related to a kind of TiO with visible light catalysis activity
2nano material, application and preparation method thereof.
Background technology
TiO
2be a kind of critical function material with broad prospect of application, there is good photocatalytic activity, be widely used in fields such as fwaater resources protections in recent years.TiO
2as photocatalyst treatment sewage, under Ultraviolet radiation condition, the organic compound of more than 3000 kind of difficult degradation of can degrading.In classes of semiconductors catalysis material, TiO
2there is biological and chemical inertia, strong anti-light and chemical attack ability, the most applicable environmental applications widely.
But TiO
2greater band gap, the TiO of anatase
2energy gap is 3.2eV, is equivalent to the energy that wavelength is 387.5nm photon, therefore TiO
2wavelength can only be effectively utilized to be less than the ultraviolet light of 387.5nm.But the ratio shared by sunshine medium ultraviolet light part only has 2% – 4%, the visible light part accounting for significant proportion in sunshine cannot be effectively utilized.Therefore, TiO is improved by various method of modifying
2visible light catalysis activity has become a study hotspot of photocatalysis field, and as metal ion mixing, nonmetal (C, N, F, S) adulterates, and the method such as noble metal loading and dye photoactivation, these researchs all achieve certain result.But most method of modifying needs to add except TiO usually
2other reagent in addition, make preparation technology become complicated, cost also can correspondingly improve.
Summary of the invention
In view of this, the invention provides a kind of TiO with visible light catalysis activity
2nano material and preparation method thereof, TiO of the present invention
2nano material not only can have stronger light absorption under the irradiation of visible ray, and its preparation technology is simple, use raw material to only have TiO
2and deionized water, do not have other reagent, do not need the reaction units such as HTHP simultaneously, equipment is simple, and easy to operate, required time is short, saves process costs largely.
For solving above technical problem, the technical scheme of first aspect provided by the invention is adopt a kind of TiO with visible light catalysis activity
2nano material, nano-grain is spherical, and the diameter of ball is 20-500nm, and the surface coverage of particle has Ti
3+and Ti-OH.
Preferably, Ti
3+be 10%-50% in the area coverage of particle surface.
Preferably, the diameter of ball is 80-300nm.
Preferably, the diameter of ball is 80-200nm.
The present invention also provides the technical scheme of second aspect and aforementioned arbitrary described TiO
2the application of nano material on visible light catalytic, described TiO
2there is light absorption phenomenon under visible light illumination in nano material.
Preferably, the wavelength of described visible ray is 380-780nm.
The present invention also provides the technical scheme of the third aspect and aforementioned arbitrary described TiO with visible light catalysis activity
2the preparation method of nano material, described preparation method carries out according to following steps: 1) prepare TiO
2suspension: by TiO
2powder joins in deionized water, and ultrasonic 1-30min, obtains TiO
2suspension; 2) laser treatment: use the laser irradiation step 1 that power is 0.01-5.0W) the middle TiO prepared
2suspension 1-500min; 3) centrifugal drying: by step 2) in use the TiO after laser treatment
2suspension, after centrifugal, outwells supernatant liquor, puts into the dry 5-24h of baking oven, finally obtains the TiO with visible light catalysis activity
2nano material.
Preferably, TiO in step 1)
2be 1:(20-100 with the mass ratio of deionized water).
Preferably, TiO in step 1)
2be 1:(50-100 with the mass ratio of deionized water).
Further preferred, TiO
2addition be preferably 10-50mg, the addition of deionized water is preferably 0.5-5g.
Preferably, step 2) in laser irradiation power be preferably 0.05W-2.0W.
Further preferred, step 2) in laser irradiation power be preferably 0.1W-0.5W.
Preferably, step 2) in laser irradiation time be preferably 60-500min.
Further preferred, step 2) in laser irradiation time be preferably 120-300min.
Preferably, step 2) described in laser be Nd:YAG laser, wavelength is 355nm.
Preferably, in step 3), oven temperature is 60-160 DEG C.
The present invention also provides the technical scheme of fourth aspect and aforementioned described TiO
2the TiO of what preparation method of nano material prepared have visible light catalysis activity
2nano material.
Preferably, nano-grain is spherical, and the diameter of ball is 20-500nm, and the surface coverage of particle has Ti
3+and Ti-OH.
Preferably, Ti
3+be 10%-50% in the area coverage of particle surface.
Preferably, the diameter of ball is 80-300nm.
Preferably, the diameter of ball is 80-200nm.
The application's gained TiO
2nano material not only can have stronger light absorption under the irradiation of visible ray, and its preparation technology is simple, use raw material to only have TiO
2and deionized water, do not have other reagent, do not need the reaction units such as HTHP simultaneously, equipment is simple, and easy to operate, required time is short, saves process costs largely.
Accompanying drawing explanation
Fig. 1 is the TiO in embodiment 1
2the photo of the ESEM (SEM) of nano material;
Fig. 2 is the TiO in embodiment 1
2the photo of the transmission electron microscope (TEM) of nano material;
Fig. 3 is the TiO in embodiment 1
2x-ray diffraction (XRD) spectrogram of nano material;
Fig. 4 is the TiO in embodiment 1
2the XPS spectrum figure of nano material;
Fig. 5 is the TiO in embodiment 1
2ultravioletvisible absorption (UV-Vis) spectrogram of nano material;
Fig. 6 is the TiO in embodiment 1
2the curve of nano material degraded rhodamine liquor;
Through the TiO of laser treatment in above accompanying drawing
2be labeled as TiO
2-NBs, untreated TiO
2raw material is labeled as TiO
2-ori.
Detailed description of the invention
In order to make those skilled in the art understand technical scheme of the present invention better, below in conjunction with detailed description of the invention, the present invention is described in further detail.
embodiment 1-TiO
2
nano material 1:
Its preparation process is as follows:
1) TiO is prepared
2suspension: by the TiO of 30mg
2powder joins in the deionized water of 0.8g, ultrasonic 1-30min.
2) laser treatment: use Nd:YAG laser, wavelength is 355nm, and power is the laser irradiation step 1 of 0.1W) the middle TiO prepared
2suspension 120min.
3) centrifugal drying: by step 2) in use the TiO after laser treatment
2suspension, after centrifugal, outwells supernatant liquor, puts into the dry 5-24h of baking oven of 60-160 DEG C, finally obtains the TiO with visible light catalysis activity
2nano material.
Fig. 1 is embodiment 1 gained TiO
2the photo of the ESEM (SEM) of nano material, as can be seen from the figure, gained TiO
2nano material is regular chondritic, and the diameter of ball is approximately 80-200nm.Fig. 2 is embodiment gained TiO
2the photo of the transmission electron microscope (TEM) of nano material, as can be seen from the figure, TiO
2nanosphere is medicine ball, and the diameter of nanosphere is consistent with ESEM acquired results.Fig. 3 is embodiment 1 gained TiO
2x-ray diffraction (XRD) spectrogram of nano material, as can be seen from the figure, gained TiO
2for anatase structured, with the TiO used
2raw material is the same.Fig. 4 is embodiment 1 gained TiO
2the XPS collection of illustrative plates of nano material, as can be seen from the figure, the TiO that laser treatment obtains
2nano-material surface defines Ti-OH and Ti
3+species.
Fig. 5 is embodiment 1 gained TiO
2ultravioletvisible absorption (UV-Vis) spectrogram of nano material.Compare the TiO as raw material
2, the TiO prepared
2nano material has very strong absorption within the scope of visible light wave range.By gained TiO
2nano material carries out visible light catalysis activity sign by photocatalytic degradation rhodamine liquor.Experimentation is as follows, is divided into two groups of experiments, carries out respectively under illumination and dark condition.Be 1.0*10 by 15mL concentration
-5the rhodamine liquor of mol/L joins in conical flask, then adds the TiO of 5mg
2nano material is as catalyst, and ultrasonic 3min, configures two parts altogether.First part and second part while under dark condition, stir 1h, respectively sampling and testing, then first part is still stirred under dark condition, and second part uses radiation of visible light, and light source is green glow diode, and voltage is 3.5V.Sampling and testing is carried out when reaction time is 1h, 2h, 3h, 4h, 5h.Sampling and testing method: reaction solution is first centrifugal, take out supernatant liquor, use ultraviolet-visible absorption spectroscopy (UV-Vis) to measure the absorbance A that rhodamine is 553nm place at wavelength, calculating absorbance A and unreacted rhodamine are the original absorbance A at 553nm place at wavelength
0ratio A/A
0, according to formula C/C
0=A/A
0, the ratio C/C of rhodamine concentration before obtaining reacted rhodamine concentration and reacting
0, then supernatant liquor is refunded in centrifuge tube and continues reaction, until sampling and testing again after reaction in 1 hour, repeatedly carry out above-mentioned steps.Under dark and illumination condition, obtain C/C respectively
0 is darkand C/C
0 illumination, final calculating Δ C/C
0=C/C
0 is dark-C/C
0 illumination.
Fig. 6 is embodiment 1 gained TiO
2the curve of nano material degraded rhodamine liquor, the TiO that laser treatment obtains
2the result that nano material obtains obviously is better than the TiO as raw material
2.After use green glow diode irradiates 5h, the TiO that laser treatment obtains
2the palliating degradation degree of nano material degraded rhodamine liquor is 33%, as the TiO of raw material
2the result of gained is 0, does not substantially degrade.
embodiment 2-TiO
2
nano material 2:
Its preparation process is as follows:
TiO is added in order to check
2amount to gained TiO
2the impact of nano material visible light catalysis activity, except TiO
2outside addition difference, other reaction condition is all identical with embodiment 1.Result shows, works as TiO
2addition be respectively 10,20,40,50,200mg and 500mg time, prepared TiO
2the palliating degradation degree of the photocatalytic degradation rhodamine liquor of nano material is respectively: 34%, 33%, 28%, 25%, 10% and 5%.Its reason may be work as TiO
2when addition is too much, the TiO that laser is irradiated to
2ratio reduce, cause the TiO of gained
2the ratio of middle laser treatment reduces, and palliating degradation degree is reduced.Therefore, there is the TiO of visible light catalysis activity
2in the preparation process of nano material, TiO
2addition be preferably 10-50mg, be further preferably 10-30mg.
For embodiment 2 and embodiment 1 gained TiO
2nano material 2 and TiO
2the structural characterization of nano material 1 and the palliating degradation degree contrast of visible light catalytic are listed as follows:
Table one:
embodiment 3-TiO
2
nano material 3:
Its preparation process is as follows:
In order to check the amount adding deionized water to gained TiO
2the impact of nano material visible light catalysis activity, except deionized water addition difference, other reaction condition is all identical with embodiment 1.Result shows, when deionized water addition 0.1,0.3,0.5,1.5,3,5g and 10g time, prepared TiO
2the palliating degradation degree of the photocatalytic degradation rhodamine liquor of nano material is respectively 5%, 10%, 30%, 33%, 34%, 33%, 25%; Its reason may be when the amount of deionized water is very few, the TiO that laser is irradiated to
2ratio reduce, cause the TiO of gained
2the ratio of middle laser treatment reduces, and palliating degradation degree is reduced.Therefore, there is the TiO of visible light catalysis activity
2in the preparation process of nano material, the addition of deionized water is preferably 0.5-5g, is further preferably 1.5-5g.
For embodiment 3 and embodiment 1 gained TiO
2nano material 3 and TiO
2the structural characterization of nano material 1 and the palliating degradation degree contrast of visible light catalytic are listed as follows:
Table two:
embodiment 4-TiO
2
nano material 4:
Its preparation process is as follows:
In order to check laser power to gained TiO
2the impact of nano material visible light catalysis activity, except laser power, other reaction condition is all identical with embodiment 1.Result shows, when laser power is respectively 0.01W, 0.05W, when 0.2W, 0.3W, 0.4W, 0.5W, 2.0W, 5.0W, and prepared TiO
2the palliating degradation degree of the photocatalytic degradation rhodamine liquor of nano material is respectively: 10%, 15%, 33%, 35%, 35%, 34%, 25%, 10%, and its reason may be when laser irradiation power is too small or too high, TiO
2the change of material surface character is not obvious, is not improved significantly to the absorbability of visible ray, so photocatalytic activity is not high.Therefore, there is the TiO of visible light catalysis activity
2in the preparation process of nano material, laser irradiation power is preferably 0.05W-2.0W, is further preferably 0.1W-0.5W.
For embodiment 4 and embodiment 1 gained TiO
2nano material 4 and TiO
2the structural characterization of nano material 1 and the palliating degradation degree contrast of visible light catalytic are listed as follows:
Table three:
embodiment 5-TiO
2
nano material 5:
Its preparation process is as follows:
In order to check laser irradiation time to gained TiO
2the impact of nano material visible light catalysis activity, except laser irradiation time, other reaction condition is all identical with embodiment 1.Result shows, when laser irradiation time is respectively 1min, when 5min, 60min, 300min, 500min, and prepared TiO
2the palliating degradation degree of the photocatalytic degradation rhodamine liquor of nano material is respectively: 0%, 10%, 20%, 34%, 34%, and its reason may be when laser irradiation time is too short, TiO
2although the change of material surface character occurs, change is complete not, is not improved significantly, so photocatalytic activity is not high to the absorbability of visible ray.Therefore, there is the TiO of visible light catalysis activity
2in the preparation process of nano material, laser irradiation time is preferably 60-500min, is further preferably 120-300min.
For embodiment 5 and embodiment 1 gained TiO
2nano material 5 and TiO
2the structural characterization of nano material 1 and the palliating degradation degree contrast of visible light catalytic are listed as follows:
Table four:
Below be only the preferred embodiment of the present invention, it should be pointed out that above-mentioned preferred embodiment should not be considered as limitation of the present invention, protection scope of the present invention should be as the criterion with claim limited range.For those skilled in the art, without departing from the spirit and scope of the present invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. one kind has the TiO of visible light catalysis activity
2nano material, is characterized in that: nano-grain is spherical, and the diameter of ball is 20-500nm, and the surface coverage of particle has Ti
3+and Ti-OH.
2. the TiO with visible light catalysis activity according to claim 1
2nano material, is characterized in that: Ti
3+be 10%-50% in the area coverage of particle surface.
3. the TiO with visible light catalysis activity according to claim 1
2nano material, is characterized in that: the diameter of ball is 80-300nm.
4. the arbitrary described TiO of claim 1-3
2the application of nano material on visible light catalytic, is characterized in that: described TiO
2there is light absorption phenomenon under visible light illumination in nano material.
5. application according to claim 4, is characterized in that: the wavelength of described visible ray is 80-780nm.
6. the TiO with visible light catalysis activity in claim 1-3 described in arbitrary claim
2the preparation method of nano material, is characterized in that, described preparation method carries out according to following steps:
1) TiO is prepared
2suspension: by TiO
2powder joins in deionized water, and ultrasonic 1-30min, obtains TiO
2suspension;
2) laser treatment: use the laser irradiation step 1 that power is 0.01-5.0W) the middle TiO prepared
2suspension 1-500min;
3) centrifugal drying: by step 2) in use the TiO after laser treatment
2suspension, after centrifugal, outwells supernatant liquor, puts into the dry 5-24h of baking oven, finally obtains the TiO with visible light catalysis activity
2nano material.
7. preparation method according to claim 6, is characterized in that: TiO in step 1)
2be 1:(20-100 with the mass ratio of deionized water).
8. preparation method according to claim 6, is characterized in that: step 2) described in laser be Nd:YAG laser, wavelength is 355nm.
9. preparation method according to claim 6, is characterized in that: in step 3), oven temperature is 60-160 DEG C.
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CN112844349A (en) * | 2019-11-28 | 2021-05-28 | 桂林理工大学 | Method for preparing TiOx photoanode by laser etching of Ti sheet |
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Application publication date: 20160302 |