CN100389879C - Synthesis method of nanometer crystal mesopore titanium dioxide photocatalyst - Google Patents
Synthesis method of nanometer crystal mesopore titanium dioxide photocatalyst Download PDFInfo
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- CN100389879C CN100389879C CNB2006100258856A CN200610025885A CN100389879C CN 100389879 C CN100389879 C CN 100389879C CN B2006100258856 A CNB2006100258856 A CN B2006100258856A CN 200610025885 A CN200610025885 A CN 200610025885A CN 100389879 C CN100389879 C CN 100389879C
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Abstract
The present invention belongs to the technical field of titanium dioxide photocatalysts, particularly to a synthesizing method of nanometer crystal mesopore TiO2 photocatalysts. The present invention uses a low temperature synthesizing route and comprises the concrete steps: under the condition of stir, non titanium alcohol salts (a titanium source) are added to non-aqueous solvents (alcohol or ether); non-aqueous gel of TiO2 is prepared by reflux and aging at certain temperature; the gel is dried after being filtered and washed and is irradiated by ultraviolet light whose irradiation wavelength is from 200 to 400 nm for certain time, and the finished products of the nanometer crystal mesopore TiO2 photocatalysts are obtained. The photocatalysts have high octahedrite phase crystallinity and large specific surface area (larger than 260m<2>. g<-1>), and display photocatalytic performance more higher than that of Degussa commercial P-25 catalysts in the experiments on environmental pollutant photocatalytic degradation. The method has the advantages of simple and easy obtained raw materials and short preparation period, and is suitable for the requirements of mass production.
Description
Technical field
The invention belongs to the titanium dioxide optical catalyst technical field, be specifically related to a kind of synthetic method of nanometer crystal mesopore titanium dioxide photocatalyst, the non-water route of particularly a kind of low temperature line synthesizes the method for high-crystallinity, Large ratio surface nanometer crystal mesopore titanium dioxide.
Technical background
In recent years, along with the maturation gradually of nanometer synthetic technology, the development and utilization of novel nano semi-conducting material is subjected to people's common concern.In numerous semi-conducting materials, titanium dioxide (TiO
2) with its avirulence, price is low and characteristics such as fast light corrosion become one of photoelectric material of the potential using value of tool.
Yet, consider nano-TiO from practical application and commercialization
2The technology of preparing of material still needs further to optimize and revise in the hope of preparing nano-TiO efficiently by approach conveniently
2Material.According to domestic and international great deal of research results in recent years, has high degree of crystallinity, big specific area and less crystallite dimension is the TiO of superior performance
2It is the prerequisite important structure feature of catalysis material.But in present preparation technology, the method that obtains this class nano-crystalline photocatalysis material adopt with the titanium alkoxide be sol-gel (sol-gel) the method knot of raw material or reverse microemulsion (Microemulsion) method close high-temperature roasting handle (Chem.Mater.1992,4:1329).The titanium alkoxide is as producing TiO on the one hand
2Raw material, cost an arm and a leg, be unfavorable for practical application.On the other hand, follow-up high-temperature roasting often causes the reunion of catalyst and reducing of specific area, is unfavorable for high activity TiO
2The exploitation of series photocatalyst.Long simultaneously manufacturing cycle and higher energy loss-rate can not adapt to the requirement of commercially producing.
What is more important, TiO
2A main application direction of nano material is the surface that is applied to host material as coating or film coating, and follow-up coating method has conveniently characteristics, but comes off easily, and caking property and life-span are not fine.Exist the main cause of this problem to be TiO
2The cohesive process of nano material and carrier is not that original position takes place.Because general matrix all is difficult to stand high-temperature roasting and handles, and crystal TiO efficiently
2Must obtain through high-temperature roasting again, so can only make TiO by the method for follow-up solvent plated film
2The nanocrystalline stromal surface that loads on.Will be from technical standpoint, the basic way that solves this contradiction is the exploitation of in-situ low-temperature coating technique, and that primarily will solve is exactly low temperature synthesizing efficient TiO
2Nanocrystalline catalyst.
Therefore, on the prior art basis, design and under cryogenic conditions, to prepare the nanocrystalline TiO of high-crystallinity Large ratio surface
2The novel synthetic of photochemical catalyst is imperative.
Summary of the invention
The object of the present invention is to provide a kind of efficient mesoporous TiO of simple and effective synthetic surface cleaning
2The method of nano-crystalline photocatalysis agent, mesoporous TiO obtained by this method
2Photochemical catalyst degree of crystallinity height, pore-size distribution homogeneous, specific area is big and crystallite dimension is little.
The present invention with the cheap more metal inorganic salt of relative titanium alkoxide (as TiCl
4) be primary raw material, by the synthetic highlight catalytic active TiO of low temperature route
2Manufacturing cycle and production cost have effectively been shortened in the nano-crystalline photocatalysis agent, can satisfy the actual demand of photocatalysis field preferably.
The mesoporous TiO of synthesizing nanocrystalline that the present invention proposes
2The method of photochemical catalyst is to adopt the non-water route of low temperature line, and its preparation concrete steps are as follows: under stirring condition, a certain amount of non-titanium alkoxide (titanium source) is added in the nonaqueous solvents (alcohol or ether), the mol ratio of nonaqueous solvents and non-titanium alkoxide is 25-3; Under 30-80 ℃ of temperature reflux digestion 3-12 hour, make TiO
2Non-aqueous gel, the non-aqueous gel filtration washing is dry at a certain temperature, used UV-irradiation again 20 minutes-12 hours, can obtain the highlight catalytic active TiO of cleaning surfaces
2The nano-crystalline photocatalysis agent.
According to the present invention, said non-titanium alkoxide (titanium source) is titanium tetrachloride (TiCl
4) or titanyl sulfate (TiOSO
4); Organic alcohol solvent is a kind of in methyl alcohol, ethanol, phenmethylol and the tert-butyl alcohol.The organic ether solvent is a kind of in ether, diethyl ether and the dimethyl ether.
According to the present invention, the gel drying temperature is 60-100 ℃ in the preparation process, and be 6 to 24 hours drying time.
According to the present invention, preparation process medium ultraviolet light irradiation wavelength is 200-400nm, and ultraviolet source power is 30-500W, and irradiation intensity is 10-120mW/cm
2, exposure time is 20 minutes to 12 hours.
According to the present invention, the synthetic system temperature should be controlled at 10-100 ℃ in the preparation process.
The TiO that the present invention obtains
2The nano-crystalline photocatalysis agent has the following advantages:
1, the nanocrystalline mesoporous TiO of cleaning surfaces that obtains of low temperature route of the present invention
2Photochemical catalyst has degree of crystallinity height, specific area greatly (greater than 260m
2G
-1), characteristics such as cleaning surfaces and crystallite dimension be little, in the degradation reaction of acetone, demonstrate the photocatalytic activity that obviously is better than the commercial photochemical catalyst of DegussaP-25.
2, low temperature route of the present invention does not need follow-up high-temperature roasting, has effectively saved the energy.The more important thing is whole process of preparation, temperature of reaction system all is controlled at below 100 ℃, for inciting somebody to action TiO efficiently
2Material directly loads on class plastics, textile and timber etc. can not the high-temperature roasting object surfaces provide effective solution.
3, low temperature path of preparing cycle weak point of the present invention can obtain having the mesoporous TiO of high photoactive finished product high-crystallinity in a few hours
2The nano-crystalline photocatalysis agent.
In a word, the present invention adopts the low temperature path of preparing to go out the efficient mesoporous TiO of high-crystallinity
2The nano-crystalline photocatalysis agent.Because the three-dimensional meso-hole structure of this catalyst prosperity and bigger surface area help the mass transfer and the absorption of reaction species.Degree of crystallinity owing to the little and higher anatase of crystallite dimension can provide more photocatalytic surfaces active sites simultaneously, makes the photocatalytic activity of this photochemical catalyst be much better than traditional nanocrystalline TiO
2Catalysis material.
Description of drawings
Fig. 1 is the TiO of the embodiment of the invention 1 gained
2The infrared diffuse figure of nano-crystalline photocatalysis agent.
Fig. 2 is the TiO of the embodiment of the invention 1 gained
2The TEM image of nano-crystalline photocatalysis agent
Fig. 3 is the TiO of the embodiment of the invention 1 gained
2The XRD figure of nano-crystalline photocatalysis agent.
The specific embodiment
Embodiment 1
With the titanium tetrachloride is the titanium source, with 4 milliliters of titanium tetrachloride (TiCl
4) dropwise join in 80 milliliters of phenmethylols, stir 15 minutes (mol ratio of phenmethylol and titanium tetrachloride is 21); Be controlled to the glue vessel temp and be 60 ℃ aging 6 hours, the gained sample filtering is separated, at 80 ℃ of dry 4h.At last with TiO
2Sample shone 8 hours down at 32W uviol lamp (254nm), promptly obtained the TiO of anatase crystal
2Nano-crystalline photocatalysis agent, its specific area are 268m
2G
-1Fig. 1 is the infrared diffuse figure of this sample, shows that sample surfaces does not have residual any organic matter.Fig. 2 is the transmission electron microscope photo of this sample, and the average crystal grain that shows sample is between 3 ~ 5 nanometers.The XRD figure spectrum of Fig. 3 shows that further this sample is the Detitanium-ore-type TiO of highly crystalline
2
The bucket column type photo catalysis reactor of design processing is voluntarily adopted in the photocatalysis experiment, and light source is near 32W uviol lamp (radiative wavelength concentrates on the 310nm).Acetone concentration is for (1600 ± 5uL/L) volumes are 7L, and catalyst amount is 0.5g.The control temperature of reactor is 25 ℃, and it is saturated to make catalyst reach absorption before reaction earlier, with 6 logical valves 1ml gas is imported gas chromatographic detection all gases component concentration at regular intervals during reaction.Blank test shows that the degradation rate of acetone is less than 4% under the condition of 2 hours ultraviolet irradiations that do not add catalyst.Analysis result shows, the degradation rate of acetone is 41% on the commercial P-25 photochemical catalyst that German Degussa company produces after 60 minutes, and the synthetic TiO of embodiment 1
2The benzene degradation rate of acetone is 85% in the nano-crystalline photocatalysis agent.Hence one can see that, the TiO that embodiment 1 synthesizes
2Its photocatalytic activity of nanocrystalline catalyst is apparently higher than commercial P-25 photochemical catalyst.
Embodiment 2
The titanium source is titanium tetrachloride (TiCl
4), solvent is the fixed alcohol of uncle, the fixed pure and mild TiCl of uncle
4Mol ratio be 6, being controlled to the glue vessel temp is 70 ℃, the control ultraviolet source is 300W high-pressure sodium lamp (characteristic wavelength 365nm), and exposure time is 1 hour, and other condition such as alcogel ageing time, baking temperature, drying time etc. are all identical with embodiment 1.The sample of preparation is the TiO of anatase phase (98%), brockite phase (2%)
2Nanocrystalline, crystallite dimension is at 4-6nm, and specific area is 285m
2G
-1Acetone photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the degradation rate of acetone is 95% on the sample that embodiment 2 synthesizes after 60 minutes.
Embodiment 3
The titanium source is titanium tetrachloride (TiCl
4), solvent is a diphenyl ether, diphenyl ether and TiCl
4Mol ratio be 12, being controlled to the glue vessel temp is 90 ℃, gelation time is 12 hours, baking temperature is 100 ℃, be 24 hours drying time, other condition is all identical with embodiment 2.The sample of preparation is the TiO of anatase phase
2Nanocrystalline, crystallite dimension is at 6-8nm, and specific area is 215m
2G
-1Acetone photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the degradation rate of acetone is 75% on the sample that embodiment 3 synthesizes after 60 minutes.
Embodiment 4
The titanium source is titanyl sulfate (TiOSO
4), solvent is an ethanol, ethanol and TiOSO
4Mol ratio be 8, being controlled to the glue vessel temp is 60 ℃, gelation time is 6 hours, the irradiation wavelength is 310nm, power is 150W, light application time is 3 hours, other condition is all identical with embodiment 1.The sample of preparation is the TiO of anatase phase
2Nanocrystalline, crystallite dimension is at 1-2nm, and specific area is 305m
2G
-1Acetone photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the degradation rate of acetone is 90% on the sample that embodiment 4 synthesizes after 60 minutes.
Embodiment 5
The titanium source is titanyl sulfate (TiOSO
4), solvent is a benzyl ether, benzyl ether and TiOSO
4Mol ratio be 15, being controlled to the glue vessel temp is 50 ℃, gelation time is 3 hours, the irradiation wavelength is 365nm, power is 500W, light application time is 1 hour, other condition is all identical with embodiment 4.The sample of preparation is the TiO of anatase phase
2Nanocrystalline, crystallite dimension is at 1-2nm, and specific area is 231m
2G
-1Acetone photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the degradation rate of acetone is 84% on the sample that embodiment 5 synthesizes after 60 minutes.
Embodiment 6
The titanium source is titanyl sulfate (TiOSO
4), solvent is a benzyl ether, benzyl ether and TiOSO
4Mol ratio be 15, being controlled to the glue vessel temp is 50 ℃, gelation time is 12 hours, the irradiation wavelength is 365nm, power is 300W, light application time is 3 hours, other condition is all identical with embodiment 5.The sample of preparation is the TiO of anatase phase
2Nanocrystalline, crystallite dimension is at 3-4nm, and specific area is 186m
2G
-1Acetone photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the degradation rate of acetone is 89% on the sample that embodiment 6 synthesizes after 60 minutes.
Embodiment 7
The titanium source is titanium tetrachloride (TiCl
4), solvent is a benzyl ether, benzyl ether and TiOSO
4Mol ratio be 15, being controlled to the glue vessel temp is 50 ℃, gelation time is 12 hours, the irradiation wavelength is 254nm, power is 60W, light application time is 8 hours, other condition is all identical with embodiment 5.The sample of preparation is an anatase and the rutile TiO of duplex grain structure mutually
2Nanocrystalline, crystallite dimension is at 5-8nm, and specific area is 162m
2G
-1Acetone photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the degradation rate of acetone is 76% on the sample that embodiment 7 synthesizes after 60 minutes.
Embodiment 8
The titanium source is titanyl sulfate (TiOSO
4), solvent is a phenmethylol, phenmethylol and TiOSO
4Mol ratio be 20, being controlled to the glue vessel temp is 70 ℃, gelation time is 9 hours, the irradiation wavelength is 310nm, power is 150W, light application time is 5 hours, other condition is all identical with embodiment 5.The sample of preparation is the TiO of anatase phase
2Nanocrystalline, crystallite dimension is at 4-5nm, and specific area is 204m
2G
-1Acetone photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the degradation rate of acetone is 91% on the sample that embodiment 8 synthesizes after 60 minutes.
Claims (3)
1. the synthetic method of mesoporous TiO 2 nano-crystalline photocatalysis agent, it is characterized in that concrete steps are as follows: under stirring condition, titanyl sulfate is added in organic solvent alcohol or the organic solvent ether, the mol ratio of organic solvent and titanyl sulfate is 25-3, under 30-80 ℃ of temperature reflux digestion 3-12 hour, make TiO
2Gel; With the gel filtration washing, dry again; Be 200-400nm with the irradiation wavelength then, power is 30-500W, and irradiation intensity is 10-120mW/cm
2Ultraviolet lighting 3-12 hour, promptly obtain the mesoporous TiO of high-crystallinity
2The nano-crystalline photocatalysis agent.
2. synthetic method according to claim 1 is characterized in that a kind of in methyl alcohol, ethanol and the tert-butyl alcohol of described organic solvent alcohol, and described organic solvent ether is a kind of in ether, diphenyl ether, benzyl ether and the dimethyl ether.
3. synthetic method according to claim 1 is characterized in that described baking temperature is 60-100 ℃, and be 4 to 24 hours drying time.
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| CN102614858B (en) * | 2012-04-01 | 2014-09-10 | 上海师范大学 | Reproducible selective adsorption-photocatalysis composite material and preparation method and application thereof |
| CN105664808B (en) * | 2016-01-13 | 2021-02-19 | 云南大学 | Method for preparing stable nano anatase titanium dioxide alcohol phase sol at low temperature |
| CN106111112B (en) * | 2016-06-24 | 2018-10-26 | 崔建中 | Load the preparation method of the aerogels of nano-titanium oxide |
| CN110444668B (en) * | 2019-06-25 | 2021-06-08 | 华南师范大学 | Preparation method of planar perovskite solar cell |
| CN114367276A (en) * | 2022-01-14 | 2022-04-19 | 华东师范大学重庆研究院 | Photocatalyst, preparation method and application thereof, and clothes washing method |
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| CN1224036A (en) * | 1998-10-30 | 1999-07-28 | 中国科学院感光化学研究所 | Titanium sol-gel paint adding nm inorganic compound particles, method for preparing same and use thereof |
| JP2000282244A (en) * | 1999-03-30 | 2000-10-10 | Kansai Research Institute | Production of titanium oxide film |
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| CN1687253A (en) * | 2005-04-07 | 2005-10-26 | 上海交通大学 | Method for preparing ultra hydrophilic coat of titanium dioxide by using titanium trichloride as precursor |
| JP2006096577A (en) * | 2004-09-28 | 2006-04-13 | Tokyo Institute Of Technology | Metal oxide film, method for producing the same, and formed article |
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2006
- 2006-04-20 CN CNB2006100258856A patent/CN100389879C/en not_active Expired - Fee Related
Patent Citations (6)
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| CN1224036A (en) * | 1998-10-30 | 1999-07-28 | 中国科学院感光化学研究所 | Titanium sol-gel paint adding nm inorganic compound particles, method for preparing same and use thereof |
| JP2000282244A (en) * | 1999-03-30 | 2000-10-10 | Kansai Research Institute | Production of titanium oxide film |
| CN1375459A (en) * | 2001-03-21 | 2002-10-23 | 中国科学院化学研究所 | Prepn. of nano TiO2 powder with high affinity |
| CN1663684A (en) * | 2004-03-02 | 2005-09-07 | 方侃 | Method for preparing nano titanium dioxide film |
| JP2006096577A (en) * | 2004-09-28 | 2006-04-13 | Tokyo Institute Of Technology | Metal oxide film, method for producing the same, and formed article |
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Non-Patent Citations (2)
| Title |
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| 低温苯甲醇醇解法制备高活性锐钛矿型纳米晶TiO2光催化剂. 朱建等.催化学报，第27卷第2期. 2006 |
| 低温苯甲醇醇解法制备高活性锐钛矿型纳米晶TiO2光催化剂. 朱建等.催化学报，第27卷第2期. 2006 * |
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