CN100435940C - Steam heat method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst - Google Patents
Steam heat method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst Download PDFInfo
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- CN100435940C CN100435940C CNB2007100518114A CN200710051811A CN100435940C CN 100435940 C CN100435940 C CN 100435940C CN B2007100518114 A CNB2007100518114 A CN B2007100518114A CN 200710051811 A CN200710051811 A CN 200710051811A CN 100435940 C CN100435940 C CN 100435940C
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Abstract
Disclosed is a steam heat method for preparing high crystallization nanocrystalline Tio2 photocatalyst, wherein tetrabutyl titanate is put into a Teflon inner liner having a capacity of 50 ml, and then the inner liner is put into a stainless steel reaction kettle having an inner liner and a capacity of 200 ml; and then distilled water is added between the two inner liners, and in the beginning, the distilled water does not contact the tetrabutyl titanate; the reaction kettle is heated to 120-200 DEG C for 1-48 hours after being sealed, here the distilled water evaporates and the water vapour contacts the tetrabutyl titanate so that the tetrabutyl titanate is hydrolyzed to produce precipitation; after the finishing of the reaction, the reaction kettle is cooled to room temperature, then the supernatant is removed, the obtained precipitation is washed by distilled water, vacuum dried, and grinded to flour of powder in turn so as to obtain high crystallization nanocrystalline Tio2 photocatalyst with a high activity. The method has the advantages of simpleness, low temperature, without template and additive agent, and the method uses water as solvent and is environment friendly. The steam heat method of the present invention can also be used for preparing high crystallization nanocrystalline transition metal oxide such as niobium oxides, zirconia, vanadium oxide, etc.
Description
Technical field
The present invention relates to prepare the steam heat method of high-crystallized nanocrystalline titanium dioxide photocatalyst, the invention still further relates to the steam heat preparing technical field of other high-crystallized nanocrystalline transition metal oxide.
Technical background
Between the nearest more than ten years, for the consideration of semiconductor light-catalyst extensive use in environmental improvement, as air cleaning, water sterilization, the improvement of toxic waste and water purify, and have in exploitation to have dropped into a large amount of research aspect each diversity semiconductor light-catalyst of highlight catalytic active.In various semiconductor light-catalysts, titanium dioxide is proved to be one of best photochemical catalyst that can be widely used in environmental improvement, because it has the biological and chemical inertia, and strong oxidability, economical and to the long-time stability of photoetch and chemical attack.Yet from practical application and commercial angle, TiO
2Photocatalytic activity must further be strengthened.In order to reach the purpose that improves photocatalytic activity, prepared TiO
2Powder must possess high-crystallinity, less crystallite dimension, meso-hole structure and high specific area.There are many existing methods to be used for preparing the TiO of nano-scale
2Powder photocatalyst, ultrasonic method for example, ultraviolet light auxiliary law, flux evaporation induced crystallization method, sol-gel process, hydro-thermal method etc.In these methods, sol-gel process is most widely used, and because of its equipment needed thereby is cheap, reaction temperature is low, product homogeneous, and purity height.The product of common this method preparation is amorphous, need calcination makes it be transformed into the anatase phase under 350 ℃ the temperature being higher than.Yet high like this temperature can cause receiving the reunion and the growth of brilliant particle, and its specific area is descended fast.For obtain having high-specific surface area, size is less receives brilliant TiO
2Powder, reducing the heat treatment temperature that changes mutually is a rational approach.This patent has proposed a kind of preparation high activity high-crystallized nanocrystalline TiO
2The effective ways of photochemical catalyst promptly come the hydrolysis butyl titanate with water vapour in 120 to 200 ℃ temperature range.
Summary of the invention
The objective of the invention is to consider the deficiency that common preparation high activity high-crystallized nanocrystalline titanium dioxide photocatalyst method exists, proposed a kind of steam heat method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst according to present domestic and international research present situation.This method is simple, low temperature, no template and additive, water are solvent, environmental friendliness.Adopting this method can prepare grain size is 7-15nm, and mesoporous aperture is 3-16nm, and specific area is 70-250m
2The high-crystallized nanocrystalline titanium dioxide photocatalyst of/g.
The technical scheme that realizes the object of the invention is:
A kind of method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst is characterized in that this method is steam heat method (experimental provision of steam heat reaction is as shown in Figure 1), and method step is followed successively by:
1st, butyl titanate is inserted in the polytetrafluoroethyllining lining, then this liner is put into another band and contrasted the big stainless steel cauldron of described polytetrafluoroethyllining lining;
2nd, add distilled water again between these two liners, during beginning, distilled water does not contact with butyl titanate;
3rd, with after the reactor sealing, reactor is heated to temperature required, kept 1 to 48 hour, make distilled water be evaporated to water vapour and butyl titanate haptoreaction, the butyl titanate hydrolysis, generation precipitates;
4th, reacted after, behind the reactor cool to room temperature, discard supernatant liquor, with the precipitation of gained distilled water cyclic washing, then in vacuum drying chamber in 30-100 ℃ dry 10-40 hour down, grind to form fine powder, promptly get the high-crystallized nanocrystalline titanium dioxide photocatalyst product.
The described method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst is: with butyl titanate 5-30 milliliter, preferred 10-20 milliliter is inserted in one 50 milliliters the polytetrafluoroethyllining lining, then this liner is put into the stainless steel cauldron of another 200 milliliters band liners, between these two liners, add the 5-80 ml distilled water again, preferred 30-60 ml distilled water, after the reactor sealing, reactor is heated to 120-200 ℃, butyl titanate hydrolysis 5-24 hour, precipitation distilled water cyclic washing, then in vacuum drying chamber in 80 ± 2 ℃ of dryings 10 hours, grind to form fine powder with agate mortar, promptly get the high-crystallized nanocrystalline titanium dioxide photocatalyst product.
The steam heat method of the said preparation high-crystallized nanocrystalline titanium dioxide photocatalyst of the present invention except that can preparing the titanium dioxide, can also prepare other high-crystallized nanocrystalline transition metal oxides as zirconia, niobium oxide, vanadium oxide etc.
The photocatalytic activity of prepared high-crystallized nanocrystalline titanium dioxide photocatalyst characterizes by the airborne acetone of photocatalytic degradation.Experimentation is as follows: TiO
2The test of the photocatalytic degradation acetone of sample is to carry out in the airtight rectangular vessel of 15L, and the initial concentration of acetone is 380 ± 20ppm.The preparation process of photochemical catalyst sample is with TiO
2It is on the culture dish of 7cm that suspension evenly is coated onto 4 diameters, with culture dish 100 ℃ down dry, it is stand-by to be cooled to room temperature then.The quality of each test specimen remains on 0.3g.During experiment culture dish is put into reactor, in reactor, inject acetone with microsyringe then.Reactor directly is connected with a drier that contains calcium chloride, so that the initial humidity in the control reactor.Before UV-irradiation, allow acetone steam and catalyst reach the adsorption-desorption balance.Measure the ultraviolet ray intensity that shines sample surfaces with ultraviolet light photometer (UV-A type, Beijing Normal University photoelectron instrument plant makes), its intensity is 2.5mW/cm
2, and the wavelength peak of ultraviolet light is 365nm.The concentration of acetone, carbon dioxide and steam is carried out online check and analysis with the infrared multiple gases monitor of optoacoustic (photoacoustic IR multigas monitor, INNOVA air tech instrumentsmodel 1312) in the reactor.TiO
2The photocatalytic activity of sample can come quantitatively characterizing by comparing each apparent reaction rate constant.The photocatalysis oxidation reaction of acetone is a pseudo first order reaction, and its kinetics equation can be expressed as: ln (C
0/ C)=and kt, k is the apparent speed constant, C
0With C be respectively concentration in the initial and course of reaction of acetone.
The characterizing method of the micro-structural of high-crystallized nanocrystalline titanium dioxide photocatalyst is: at Cu K α is that X-ray source, sweep speed are 0.05 ° of s
-1X-ray diffractometer (HZG41/B-PC type) on X-ray diffraction (XRD) spectrogram that obtains determine crystalline phase and crystallite dimension.The specific area of powder sample is that the method by nitrogen absorption is to test on the n2 absorption apparatus device of Micromeritics ASAP2020 (USA) in model.All samples all outgased 2 hours down at 100 ℃ earlier before test.The Brunauer-Emmett-Teller of sample (BET) surface area (S
BET) be to utilize relative pressure (P/P by the method for multiple spot BET
0) be that the interior adsorpting data of 0.05～0.3 scope calculates.Desorption isotherm is used for measuring pore-size distribution, and by Barret-Joyner-Halender (BJH) method, and the supposition hole is the cylindrical shape hole.With relative pressure (P/P
0) be that 0.994 nitrogen adsorption volume is determined pore volume and average pore size.(JEOL-2010F 200kV) observes the size and dimension of crystal grain for utilization transmission electron microscope (TEM) and high-resolution-ration transmission electric-lens (HRTEM).Observe the required sample of TEM and be at first under ultrasound condition TiO
2Powder is distributed in the absolute ethyl alcohol, then dispersant liquid drop is added to prepare on charcoal-copper composite web.
Description of drawings
Fig. 1 reaction unit schematic diagram
Fig. 2 reacts the TiO of preparation in 10 hours under different temperatures
2The XRD figure of sample
Fig. 3 reacts the TiO of preparation in 10 hours under different temperatures
2Nitrogen adsorption-the desorption isotherm of sample
Fig. 4 reacts the TiO of preparation in 10 hours under different temperatures
2The pore size distribution curve of sample
Fig. 5 is at 200 ℃ of TiO that react preparation in 10 hours down
2TEM of powder (a and b) and HRTEM (c)
The specific embodiment
Embodiment 1:
Receive brilliant TiO in order to prepare
2Powder, butyl titanate are used as the titanium source.The experimental provision of steam heat reaction as shown in Figure 1.The detailed experiments process is as follows: 15 milliliters of butyl titanates are inserted in one 50 milliliters the Teflon liner, then this liner is put into the stainless steel cauldron of another band liner of 200 milliliters.Between these two liners, add 40 ml distilled waters again.During beginning, distilled water does not contact with butyl titanate.After the sealing, reactor is heated to 120 to 200 ℃, and under this temperature, kept 10 hours.In the course of reaction, distilled water will evaporate.Water vapour can contact with butyl titanate, causes hydrolysis, the generation precipitation of butyl titanate then.Behind the reactor cool to room temperature, discard the upper strata stillness of night, with the precipitation of gained distilled water cyclic washing, then in vacuum drying chamber in 80 ℃ dry 10 hours down, at last desciccate is ground to form fine powder with agate mortar, promptly get the required brilliant TiO that receives
2Powder sample.
Characterize the phase structure of prepared sample with XRD.The TiO that under different temperatures, prepares
2The XRD figure of sample is shown in Fig. 2 and table 1 with relevant physical property.All diffraction maximums can easily be demarcated and are TiO as can see from Figure 2
2Pure anatase phase (JCPDS No.21-1272, space group: I4
1/ amd (141)).Along with the increase of reaction temperature, the diffraction peak intensity of anatase phase increases, and the diffraction peak width of (101) crystal face narrows down gradually, and the increase of degree of crystallinity and the increase of crystallite dimension are described.Studies show that further reaction temperature is to TiO
2Degree of crystallinity tangible influence is arranged.The TiO that comes out with the half-peak breadth data computation of (101) diffraction maximum according to the Scherrer equation
2The crystallite dimension of powder is listed in table 1.Prepared as can be seen from the table TiO
2The crystallite dimension of powder increases along with the increase of reaction temperature.
Fig. 3 has provided the nitrogen adsorption-desorption isotherm of 10 hours samples of reaction under the different temperatures.Under 120 ℃, thermoisopleth is the combination (BDDT classification) of I type and IV type, and two hysteresis winding are arranged, and shows and contains micropore and mesoporous in the sample, and have bimodal pore size distribution in mesoporous scope.
Fig. 4 has provided the pore size distribution curve of reaction preparation in 10 hours sample correspondence under the different temperatures.120 ℃ of samples that prepare down present three peak pore-size distributions in micropore and mesoporous scope.Two kinds of mesoporous existence are arranged in the sample, lay respectively at about 3-4nm and 5-9nm.These mesoporous may be from the hole of intercrystalline aggregate.In addition, contain micropore in the sample, may come from amorphous TiO residual in the sample
2Along with the increase of reaction temperature, pore-size distribution is distributed by three peaks and changes Unimodal Distribution gradually into, and the aperture peak value moves right.The pore-size distribution change is moved with the aperture peak value may be because of different (the seeing Fig. 2 and table 1) of degree of crystallinity.The specific area of sample reduces along with the increase of reaction temperature is dull as can be seen from Table 1, and on the contrary, because the growth of crystal grain, the aperture increases.Studies show that further pore volume and porosity also increase along with the rising of reaction temperature.This may be owing to be filled into TiO
2Amorphous TiO in mesoporous
2The content minimizing causes.
Fig. 5 has provided 200 ℃ of TiO of reaction preparation in 10 hours down
2The TEM of sample and HRTEM photo.The as can be seen from the figure spherical in shape and Size Distribution of particle relatively evenly (Fig. 5 a and b).The average-size of the primary granule of estimating from the TEM photo is approximately 12 ± 1nm, with coincide very much from the value (12.7nm) of XRD figure usefulness Scherrer equation calculating (as shown in table 1).HRTEM photo (Fig. 5 c) clearly illustrates that freshly prepd height of specimen crystallization.And one group clearly lattice fringe run through whole particle, further proved the height crystallization of particle.The spacing of lattice fringe is 0.35nm, with anatase TiO mutually
2(101) spacing of crystal face matches.
Table 2 has provided under UV-irradiation reaction temperature to prepared TiO
2The influence of the apparent reaction rate constant of powder.To 120 ℃ of TiO that prepare down
2Sample, it has bigger specific area, but its photocatalytic activity is minimum.This is because the TiO of 120 ℃ of preparations
2The powder crystallization degree is low and may contain amorphous TiO
2Cause.When reaction temperature reaches 150 ℃, photocatalytic activity obviously increases.Further improve reaction temperature, photocatalytic activity increases a little.In the time of 200 ℃, prepared powder demonstrates the highest photocatalytic activity, apparently higher than the P25 that is celebrated with highlight catalytic active.Be higher than 10 hours prepared TiO of 150 ℃ of reactions by this method
2The photocatalytic activity of powder has all surpassed P25, and this may be because these receive brilliant TiO
2Particle has bigger specific area, and littler crystallite dimension and the purity of Geng Gao etc. causes.Specific area and the crystallite dimension of P25 are respectively 50m
2/ g and 30nm.
Embodiment 2:
In order to check the influence of reaction time to the sample photocatalytic activity, reaction temperature is fixed on 200 ℃, except that the reaction time difference, other reaction condition as: the amounts of butyl titanate and water etc. are all identical with embodiment 1.The result shows that the sample that prepared at 1 hour is owing to its impalpable structure (seeing Table 1), and it does not have photocatalytic activity basically.3,5, the photocatalytic activity of the sample of preparation in 10,24 and 48 hours is shown in Table 3.Because the degree of crystallinity of the sample of preparation in 3 hours is lower, so it has shown relatively low photocatalytic activity.Along with the reaction time is increased to 5 hours, the photocatalytic activity of sample obviously increases and is higher than P25, and this may be because the former has bigger specific area, higher pore volume and littler crystallite dimension.The photocatalytic activity of the sample of preparation in 10 hours is the highest.Though this sample has bigger crystallite dimension and littler specific area than the sample of preparation in 5 hours, it has higher degree of crystallinity (seeing Table 1).Usually degree of crystallinity is high more, that is to say that defective is few more mutually with body on the surface, causes the recombination probability in light induced electron and hole to reduce increase with photocatalytic activity.Along with the further increase of reaction temperature, photocatalytic activity reduces, and this is possible be because the increase of crystallite dimension and reducing of specific area and pore volume.Can reason out according to above result and to have more high-crystallinity and the more TiO of large pore volume
2Particle more helps light-catalysed application.
Embodiment 3:
For the influence of the amount of checking butyl titanate to the sample photocatalytic activity, except that the amount difference of butyl titanate, other reaction condition as: the amounts (40 milliliters) of reaction temperature (180 ℃), reaction time (10 hours), water etc. are all identical with embodiment 1.The result shows, when the amount of butyl titanate during in 5-30 milliliter scope, prepared titanium dioxide sample all presents the high-crystallized nanocrystalline structure, and has good photocatalytic activity.The amount of finding best butyl titanate in the experiment is the 10-20 milliliter.
Embodiment 4:
For the influence of the amount of checking water to the sample photocatalytic activity, outside the amount difference that dewaters, other reaction condition as: the amounts (15 milliliters) of reaction temperature (180 ℃), reaction time (10 hours), butyl titanate etc. are all identical with embodiment 1.The result shows, when the amount of water during in 5-80 milliliter scope, prepared titanium dioxide sample all presents the high-crystallized nanocrystalline structure, and has good photocatalytic activity.The amount of finding best water in the experiment is the 30-60 milliliter.
Embodiment 5:
High-crystallized nanocrystalline transition metal oxide such as niobium oxide also can pass through method for preparing.Also be by with 15 milliliters of niobic acid ethyl ester (Nb (OC
2H
5)
4) insert in one 50 milliliters the Teflon liner, then this liner is put into the stainless steel cauldron of another band liner of 200 milliliters.Between these two liners, add 40 ml distilled waters again.During beginning, distilled water does not contact with the niobic acid ethyl ester.After the sealing, reactor is heated to temperature required (180 ℃) and under this temperature, kept 20 hours.In the course of reaction, distilled water will evaporate.Water vapour can contact with the niobic acid ethyl ester, causes the hydrolysis of niobic acid ethyl ester then.Behind the reactor cool to room temperature, discard the upper strata stillness of night, with the precipitation of gained distilled water cyclic washing, following dry 10 hours in 80 ℃ in vacuum drying chamber then, at last sample is ground to form fine powder with agate mortar, promptly get high-crystallized nanocrystalline niobium oxide powder sample.
Table 1 steam heat temperature and time is to TiO
2The influence of the physical property of sample
a
| Temperature. (℃) | Time (hour) | Specific surface (m 2/g) | Pore volume (cm 3/g) | Average pore size (nm) | Porosity (%) | Crystallite dimension (nm) |
| 120 | 10 | 250.4 | 0.177 | 2.82 | 40.8 | 7.6(1.00) |
| 150 | 10 | 140.7 | 0.278 | 7.90 | 52.1 | 9.6(1.62) |
| 180 | 10 | 119.6 | 0.358 | 12.0 | 58.3 | 10.1(2.12) |
| 200 | 10 | 92.5 | 0.365 | 15.8 | 58.8 | 12.7(2.54) |
| 200 | 1 | 253.3 | 0.125 | 1.97 | 32.8 | Amorphous |
| 200 | 3 | 121.4 | O.162 | 5.34 | 38.8 | 9.9(2.13) |
| 200 | 5 | 118.7 | 0.284 | 9.56 | 52.6 | 11.2(2.25) |
| 200 | 24 | 89.4 | 0.339 | 15.2 | 57.0 | 13.0(2.74) |
| 200 | 48 | 71.2 | 0.270 | 15.1 | 51.3 | 14.8(2.99) |
All samples is the anatase phase in the table 1; The BET surface area is by the linear segment (P/P of adsorption isotherm
0=0.05-0.3) calculate; Pore volume (total pore volume) is from P/P
0=0.994 N
2Adsorption volume obtains; Average pore size is with desorption isotherm and the estimation of Barrett-Joyner-Halenda (BJH) method; Porosity is estimated by pore volume;
fTiO
2Average grain size calculate with the Scherrer equation by XRD; Relative crystallinity: the relative intensity of anatase phase (101) crystal face diffraction maximum (be shown in the bracket, reference sample be prepared in 120 ℃ 10 hours).
Table 2 steam heat temperature (time is 10 hours) is to TiO
2The influence of the apparent reaction rate constant of sample
| The steam heat temperature/℃ | 120 | 150 | 180 | 200 | P25 |
| Apparent reaction rate constant/10 -3Minute -1 | 2.91 | 10.17 | 11.35 | 13.97 | 3.03 |
The table 3 steam heat time, (temperature is 200 ℃) was to TiO
2The influence of the apparent reaction rate constant of sample
| Steam heat time/hour | 1 | 3 | 5 | 10 | 24 | 48 |
| Speed constant/10 -3Minute -1 | 1.26 | 2.85 | 5.3 | 13.97 | 6.37 | 5.47 |
Claims (6)
1, a kind of method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst is characterized in that this method is the steam heat method, and method step is followed successively by:
1st, butyl titanate is inserted in the polytetrafluoroethyllining lining, then this liner is put into another band and contrasted the big stainless steel cauldron of described polytetrafluoroethyllining lining;
2nd, add distilled water again between these two liners, during beginning, distilled water does not contact with butyl titanate;
3rd, with after the reactor sealing, reactor is heated to temperature required, kept 1 to 48 hour, make distilled water be evaporated to water vapour and butyl titanate haptoreaction, the butyl titanate hydrolysis, generation precipitates;
4th, reacted after, behind the reactor cool to room temperature, discard supernatant liquor, with the precipitation of gained distilled water cyclic washing, then in vacuum drying chamber in 30-100 ℃ dry 10-40 hour down, grind to form fine powder, promptly get the high-crystallized nanocrystalline titanium dioxide photocatalyst product.
2, the method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst as claimed in claim 1, it is characterized in that: 5-30 milliliter butyl titanate is inserted in one 50 milliliters the polytetrafluoroethyllining lining, then this liner is put into the stainless steel cauldron of another 200 milliliters band liners, between these two liners, added the 5-80 ml distilled water again.
3, the method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst as claimed in claim 1, it is characterized in that: 10-20 milliliter butyl titanate is inserted in one 50 milliliters the polytetrafluoroethyllining lining, then this liner is put into the stainless steel cauldron of another 200 milliliters band liners, between these two liners, added the 30-60 ml distilled water again.
4, prepare the method for high-crystallized nanocrystalline titanium dioxide photocatalyst as described each of claim 1-3, it is characterized in that described reactor is heated to 120-200 ℃.
5, prepare the method for high-crystallized nanocrystalline titanium dioxide photocatalyst as described each of claim 1-3, it is characterized in that the described reaction time is 5-24 hour.
6, prepare the method for high-crystallized nanocrystalline titanium dioxide photocatalyst as described each of claim 1-3, the temperature that it is characterized in that described drying is 80 ± 2 ℃, and be 10 hours drying time.
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| CN105905943A (en) * | 2016-06-30 | 2016-08-31 | 太原理工大学 | Preparation method of mesoporous zirconium dioxide nanocrystals |
| CN110156073B (en) * | 2018-01-31 | 2021-09-17 | 安徽大学 | Preparation of TiO by steam hot solution evaporation2Method (2) |
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| CN109354062A (en) * | 2018-11-26 | 2019-02-19 | 昆明冶金研究院 | A kind of nanometer anatase titania and the preparation method and application thereof |
| CN109704402A (en) * | 2018-12-10 | 2019-05-03 | 长安大学 | A kind of synthetic method of the ultra-fine uniform cubic zirconia nanocrystals body material of ambient-temp-stable |
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| CN110252375B (en) * | 2019-06-25 | 2021-06-29 | 长安大学 | Iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound, preparation method and application as photocatalyst |
| CN111533167B (en) * | 2020-05-12 | 2023-03-31 | 鑫统领建材集团有限公司 | Preparation method of modified titanium dioxide, modified titanium dioxide and application |
| CN113333009B (en) * | 2021-05-29 | 2022-02-18 | 安徽大学 | Nitrogen-doped gamma-Bi2MoO6Method for preparing photocatalyst |
| CN113333010B (en) * | 2021-05-29 | 2022-02-18 | 安徽大学 | Photocatalyst nitrogen-doped SrMoO4Preparation method of (1) |
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