CN1810356A - Prepn process of nanometer crystal titania aerogel with high photocatalysis activity - Google Patents
Prepn process of nanometer crystal titania aerogel with high photocatalysis activity Download PDFInfo
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- CN1810356A CN1810356A CN 200610024301 CN200610024301A CN1810356A CN 1810356 A CN1810356 A CN 1810356A CN 200610024301 CN200610024301 CN 200610024301 CN 200610024301 A CN200610024301 A CN 200610024301A CN 1810356 A CN1810356 A CN 1810356A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- 239000013078 crystal Substances 0.000 title claims abstract description 11
- 238000007146 photocatalysis Methods 0.000 title abstract description 18
- 230000000694 effects Effects 0.000 title abstract description 7
- 239000004964 aerogel Substances 0.000 title abstract description 6
- 238000000034 method Methods 0.000 title description 11
- 239000010936 titanium Substances 0.000 claims abstract description 46
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 150000002924 oxiranes Chemical class 0.000 claims abstract description 13
- 238000000352 supercritical drying Methods 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 11
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 7
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000004703 alkoxides Chemical class 0.000 claims description 7
- 239000002159 nanocrystal Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 40
- -1 titanium alkoxide Chemical class 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 abstract 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 24
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 22
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000001294 propane Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 2
- 241001296405 Tiso Species 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000006037 cell lysis Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000011468 face brick Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005348 self-cleaning glass Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The preparation process of aerogel TiO2 with high photocatalysis activity includes the following steps: dissolving non-titanium alkoxide and titanium source in alcohol-water mixture solution through stirring; adding metered epoxide to obtain translucent lumpy alcohol gel of titanium oxide in minutes; ageing, supercritical drying and roasting to obtain nanometer crystal aerogel TiO2 block or powder with adjustable micro structure and specific surface area greater than 100 sq m/g. Where, the titanium source is titanium tetrachloride, titanium trichloride or titanium sulfate; the epoxide is ethylene oxide, propylene oxide, chloropropylene oxide or butylenes oxide; and the organic alcohol solvent is methanol, ethanol, isopropanol or tert-butyl alcohol. When used in degrading nitrobenzene and other sewage treatment, the aerogel TiO2 has photocatalysis activity as high as three times that of commercial P-25 photocatalyst.
Description
Technical field
The present invention relates to the preparation method of high-activity nano crystal titanium dioxide powder semiconductor light-catalyst, the method for a kind of non-titanium alkoxide sol-gel path of preparing nanometer crystal titania aerogel is provided especially.
Technical background
Titanium dioxide (TiO
2) the catalysis material prospect that has a very wide range of applications in storage of solar energy and utilization, photochemistry conversion, organic pollution processing, sterilization and fields such as sterilization and ecological architectural material, thereby caused the extensive interest and the concern of countries in the world governments, branch of industry and academia.Recent decades, especially over past ten years, conductor photocatalysis material has become the focus and emphasis of countries in the world scientists study, and more and more about the research paper and the patent of this respect, annual all have thousands of pieces research work to deliver.In actual applications, TiO
2Catalysis material has been used for the fields such as purifier, self-cleaning glass surface, antibiotic photocatalysis ceramics face brick, solar cell and photolysis water hydrogen of water and air, has produced huge economy, environment and social benefit.
Yet, consider TiO from practical application and commercialization
2The activity of photochemical catalyst still is further improved and improves.TiO
2Photochemical catalyst is the same with other catalysis materials, all needs big specific area and little crystallite dimension, so that there is more chain carrier to participate in reaction.For reaching this purpose, design and prepare have high degree of crystallinity, the TiO of little crystallite dimension and high specific area
2Photochemical catalyst is necessary and necessary.At various preparation TiO
2In the method for nanocrystal, with titanium alkoxide such as tetraethyl titanate, isopropyl titanate and butyl titanate be sol-gel (sol-gel) method of raw material be widely adopted (Chem.Mater.1992,4:1329).This method has advantages such as equipment less investment, preparation condition gentleness, but also exists cost of material height, preparation parameter complexity, manufacturing cycle length and product quality to be difficult to deficiencies such as control.The common TiO of preparation in this way
2Be unformed shape at first, be with TiO
2Be transformed into the anatase or the rutile phase of crystalline state from unformed shape, must make further high-temperature heat treatment it.Along with the raising of heat treatment temperature, TiO
2Degree of crystallinity improve TiO
2Photocatalytic activity strengthened.But then, the raising of heat treatment temperature will cause TiO
2The decline of grain growth and specific area, thus its photocatalytic activity reduced greatly.
For obtaining nanocrystalline TiO with high-ratio surface and little crystallite dimension
2Photochemical catalyst, a feasible and rational approach is the nanocrystalline aeroge TiO that design and preparation have high thermal stability
2Aeroge TiO
2Not only specific area height, bulk density are low, and have unique nanometer three dimensions packed structures, the mass transfer that helps reacting and can providing than conventional Ti O
2The more chain carrier of photochemical catalyst participates in reaction, thereby strengthens its photocatalytic activity greatly.Have the high-performance optical catalysis material of potential application foreground, aeroge TiO in recent years as a class
2The preparation of catalysis material, sign and application study receive much attention (J Phys Chem B, 1997,101 (19): 3746; Chem Lett, 2004,33 (5): 574; J PhotochemPhotobiol, A 2005,172:19).With titanium alkoxide such as butyl titanates is raw material, adopts traditional sol-gel process can obtain aeroge TiO in conjunction with Supercritical Drying Technology
2, this technology not only manufacturing cycle is long, and usually needs to cost an arm and a leg and the unmanageable titanium alkoxide of hydrolytic process is presoma (J Non Cryst Solids, 2004,350:314; J Mol CatalA, 2005,229 (1-2): 145).Non-titanium alkoxide precursor (titanium tetrachloride, titanium trichloride, titanium sulfate etc.) cheap and easy to get is preparation aeroge TiO
2Desirable feedstock, be that the sol-gel process of hydrolytic accelerating agent prepares the intact alcogel of quality but be difficult to adopt traditional with common mineral acid or alkali, more can't further obtain the block aeroge TiO that quality is intact and structural property is easy to regulate and control
2
Summary of the invention
The objective of the invention is to the shortcoming that exists at prior art, provide a kind of simple and very effective preparation to have the brilliant TiO of highlight catalytic active nano
2The method of photochemical catalyst makes the TiO that makes
2Photochemical catalyst has that specific surface is big, crystallite dimension is little and characteristics such as crystalline phase is adjustable, to satisfy the actual demand of photocatalysis field.
Nanocrystalline TiO of the present invention
2Photochemical catalyst be a kind of non-titanium alkoxide sol-gel path of preparing obtain receive brilliant TiO
2Aeroge, its preparation method comprises the steps: earlier non-titanium alkoxide titanium source to be dissolved in the one-tenth glue container that is equipped with organic alcohol and water mixed solution, stirs, and adds the epoxides of metering then, continue to stir, until obtaining the block alcogel of translucent titanium oxide; Again further through aging, supercritical drying and calcination process step, but finally obtain the nanocrystalline aeroge TiO of grain size, pore structure and crystal formation modulation
2Block or powder.
Among the present invention, being controlled to glue container interior reaction temperature is 0-80 ℃.The aging of resulting alcogel at room temperature carries out ageing time 1-12 hour.Said supercritical drying is the overcritical or high temperature ethanol supercritical drying of low-temperature carbon dioxide, to remove water and the organic alcohol solvent in the alcogel, obtains aeroge.Said aeroge calcination process is at 300-800 ℃ of following roasting 2-8 hour, by control sintering temperature and roasting time can obtain anatase mutually with the rutile different single-phase or biphase nanocrystalline aeroge TiO of crystalline phase composition mutually
2Photochemical catalyst.
Among the present invention, said non-titanium alkoxide titanium source is selected from titanium tetrachloride (TiCl
4), titanium trichloride (TiCl
3), titanium sulfate (TiSO
4) in a kind of; Epoxides is any in oxirane, expoxy propane, epoxychloropropane and the epoxy butane; Organic alcohol solvent is any in methyl alcohol, ethanol, isopropyl alcohol and the tert-butyl alcohol.
Among the present invention, said mixed solution, the volume ratio of its organic alcohol solvent and water is 5: 1-20: 1, the mol ratio in water and non-titanium alkoxide titanium source is 2-10, the mol ratio in the epoxides of adding and titanium source is 4-10.
The nanocrystalline aeroge TiO of the present invention
2Photochemical catalyst has the following advantages,
1, non-titanium alkoxide sol of the present invention-gel route obtains receives brilliant aeroge TiO
2Photochemical catalyst has that specific surface is big, crystallite dimension is little, crystalline phase is adjustable and characteristics such as heat endurance height, in sewage disposals such as nitrobenzene degradation reaction, demonstrates than the commercial photochemical catalyst of Degussa P-25 up to nearly photocatalytic activity more than three times.
2, the present invention can make macro-size for millimeter to the block aeroge sample of Centimeter Level, in fields such as sewage disposal than traditional TiO such as Degussa P-25
2More easily separated and the recovery of manocrystalline powders sample.
3, the non-titanium alkoxide sol of the present invention-gel path of preparing cycle weak point can obtain having high photoactive bulk or Powdered finished product aeroge TiO in a few hours
2Photochemical catalyst.
In a word, the present invention adopts non-titanium alkoxide sol-gel route to prepare in conjunction with supercritical drying that the Large ratio surface crystalline phase is regulatable receives brilliant aeroge TiO
2Powder.Because nanocrystalline aeroge TiO
2Be the open three dimensional pore passage structure, the mass transfer that helps reactant in the liquid phase photocatalytic process, simultaneously, make the photocatalytic activity of this type of aeroge photochemical catalyst be much better than traditional nanocrystalline TiO because crystallite dimension is little and Large ratio surface can provide the synergy of factor such as more photocatalytic surfaces active sites
2Catalysis material.
Description of drawings
Fig. 1 is the unfired block TiO of the different size of the embodiment of the invention 1 gained
2The optical photograph of aeroge.
Fig. 2 is the nanocrystalline TiO of the embodiment of the invention 1 gained
2The TEM image of aeroge sample and feature electronic diffraction ring.
The specific embodiment
Block or the Powdered nanocrystalline aeroge TiO that synthesizes according to the present invention
2Have good photocatalytic activity, the invention will be further described below by each embodiment:
Be that gelatinizing agent prepares bulk and receives brilliant aeroge TiO with the expoxy propane
2The method of photochemical catalyst is as follows: be the titanium source with the titanium tetrachloride, with 2 milliliters of titanium tetrachloride (TiCl
4) be added drop-wise in the mixed solution of 20 milliliters of absolute ethyl alcohols and 1 ml distilled water composition, the mol ratio of water and titanium tetrachloride is 3, stirs 15 minutes; Being controlled to glue container reaction temperature is 25 ℃; Add 3.5 milliliters of expoxy propane fast, the mol ratio of expoxy propane and titanium tetrachloride is 5, stirs and obtains block titanium oxide alcogel after 3-5 minute; Wore out 2 hours under the room temperature, under nearly room temperature CO 2 supercritical condition, obtaining block TiO subsequently
2Aeroge (Fig. 1).At last should bulk aeroge TiO
2400 ℃ of following roastings 4 hours, obtain the brilliant aeroge TiO of lumpy nanometer of anatase crystal
2, its specific area is 126m
2G
-1Fig. 2 is the transmission electron microscope photo of this sample, and as seen from the figure, the average crystal grain size is between 30 ~ 50 nanometers.Electronic diffraction ring in the illustration shows that further this sample is the Detitanium-ore-type TiO of highly crystalline
2
The quartzy photo catalysis reactor of bucket column type of design processing is voluntarily adopted in the photocatalysis experiment, and central light source is near 32W high-pressure sodium lamp (radiative wavelength concentrates on the 254nm).Nitrobenzene reactant liquor (4.00 * 10
-3Mol/L) volume is 500mL, and catalyst amount is 0.5g.Before reaction,, catalyst is dispersed in the reactant liquor earlier with ultrasonic wave dispersed catalyst (20min).The control temperature of reactor is 25 ℃, and by reactant liquor bottom bubbling air (flow velocity 80mL/min), electromagnetic agitation is dispersed in the reactant liquor catalyst during reaction.The 5mL that behind the light-catalyzed reaction certain hour, takes a sample, centrifugal, filter the back according to utilizing remaining nitro phenenyl concentration in high pressure liquid chromatography (HPLC) the analytical reactions liquid, calculate nitrobenzene clearance in the photocatalytic degradation reaction according to this result.Blank test shows that the degradation rate of nitrobenzene is less than 4% under the condition of 2 hours ultraviolet irradiations that do not add catalyst.Analysis result shows, the nitrobenzene clearance is 32% on the commercial P-25 photochemical catalyst that German Degussa company produces after 40 minutes, and the synthetic nanocrystalline TiO of embodiment 1
2The nitrobenzene clearance is 92% on the aeroge sample.Hence one can see that, the nanocrystalline TiO of aeroge that embodiment 1 synthesizes
2Have than commercial P-25 photochemical catalyst up to nearly photocatalytic activity more than three times.
Embodiment 2
The titanium source is titanium tetrachloride (TiCl
4), epoxides is an epoxychloropropane, organic alcohol solvent is an isopropyl alcohol, water and TiCl
4Mol ratio be 6, being controlled to glue container reaction temperature is 0 ℃, other condition such as titanium source concentration, solvent and epoxychloropropane are all identical with embodiment 1 with respect to titanium source consumption, alcogel ageing time, sintering temperature and time etc.Nearly room temperature CO 2 supercritical condition drying makes block unformed TiO
2Aeroge.Sample is pulverized the back and obtained specific area in 6 hours in 500 ℃ of roastings is 101m
2G
-1The nanocrystalline aeroge TiO of Powdered anatase crystal
2Nitrobenzene photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the nitrobenzene clearance is 85% on the sample that embodiment 2 synthesizes after 40 minutes.
Embodiment 3
The titanium source is titanium tetrachloride (TiCl
4), epoxides is an epoxychloropropane, organic alcohol solvent is a methyl alcohol, water and TiCl
4Mol ratio be 6, being controlled to glue container reaction temperature is 80 ℃, under the alcogel room temperature aging 12 hours, other condition such as titanium source concentration, solvent and epoxychloropropane be with respect to titanium source consumption, sintering temperature and time etc. are all identical with embodiment 1.Nearly room temperature CO 2 supercritical condition drying makes block unformed TiO
2Aeroge, 700 ℃ of roastings be after 6 hours, obtains anatase and rutile ratio and be respectively 80 and 20 the nanocrystalline aeroge TiO with duplex grain structure
2, specific area is 71m
2G
-1Nitrobenzene photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the nitrobenzene clearance is 97% on the sample that embodiment 3 synthesizes after 40 minutes.
Embodiment 4
The titanium source is titanium tetrachloride (TiCl
4), epoxides is an expoxy propane, water and TiCl
4Mol ratio be 10, the mol ratio in expoxy propane and titanium source is 7, ageing time is 8 hours, other condition such as titanium source concentration, etoh solvent, sintering temperature is all identical with embodiment 1 with time etc.The unformed aeroge TiO of the dry obtained bulk of nearly room temperature CO 2 supercritical condition
2, 800 ℃ of roastings are after 3 hours, obtain anatase and rutile ratio and are respectively 30 and 70 the nanocrystalline TiO with duplex grain structure
2Aeroge, specific area are 21m
2G
-1Nitrobenzene photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the nitrobenzene clearance is 57% on the sample that embodiment 3 synthesizes after 40 minutes.
Embodiment 5
Except that institute's water consumption, other condition such as titanium source concentration, water and TiCl
4Actual use amount, expoxy propane is with respect to titanium source consumption, sintering temperature is all identical with embodiment 1 with time etc.The volume ratio of etoh solvent and water is 5; Ethanol super critical condition drying directly makes Powdered anatase type nano crystal aeroge TiO
2, specific area is up to 348m
2G
-1Nitrobenzene photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the nitrobenzene clearance is 77% on the sample that embodiment 5 synthesizes after 40 minutes.
Embodiment 6
Except that institute's water consumption, other condition such as titanium source concentration, water and TiCl
4Actual use amount, expoxy propane is with respect to titanium source consumption, sintering temperature is all identical with embodiment 5 with time etc.The volume ratio of etoh solvent and water is 5; Ethanol super critical condition drying directly makes Powdered anatase type nano crystal aeroge TiO
2, further in 500 ℃ of roastings after 8 hours, specific area is 240m
2G
-1Nitrobenzene photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the nitrobenzene clearance is 89% on the sample that embodiment 6 synthesizes after 40 minutes.
Embodiment 7
The titanium source is titanium trichloride (TiCl
3), epoxides is an oxirane, ageing time 5 hours, and other preparation and supercritical drying condition are identical with embodiment 1, and the unformed aeroge sample of gained pulverizes and 300 ℃ of roastings 8 hours, making specific area was 87m
2G
-1Powdered anatase type nano crystal aeroge TiO
2Nitrobenzene photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the nitrobenzene clearance is 39% on the sample that embodiment 7 synthesizes after 40 minutes, and is suitable with the photocatalytic activity of commercial P-25 photochemical catalyst.
Embodiment 8
The titanium source is titanium trichloride (TiCl
3), epoxides is the chloro expoxy propane, other preparation parameters and supercritical drying condition are identical with embodiment 1, and the unformed block aeroge sample of gained is pulverized the back in 600 ℃ of roastings 8 hours, make anatase and rutile ratio and are respectively 90 and 10 the nanocrystalline aeroge TiO with duplex grain structure
2, specific area is 47m
2G
-1Nitrobenzene photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the nitrobenzene clearance is 79% on the sample that embodiment 8 synthesizes after 40 minutes.
Embodiment 9
The titanium source is titanium trichloride (TiCl
3), epoxides is the chloro expoxy propane, chloro expoxy propane and TiCl
3Mol ratio be 8, solvent is the tert-butyl alcohol, other preparation parameters and supercritical drying condition are identical with embodiment 6, gained aeroge sample is further through 400 ℃ of roastings 2 hours, making specific area is 132m
2G
-1Anatase nanometer crystal aeroge TiO
2Sample.Nitrobenzene photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the nitrobenzene clearance is 87% on the sample that embodiment 9 synthesizes after 40 minutes.
Embodiment 10 titanium sources are titanium sulfate (TiSO
4), epoxides is an epoxy butane, solvent is an isopropyl alcohol, the volume ratio of isopropyl alcohol and water is 20, the mol ratio in epoxy butane and titanium source is 6, other preparation parameters and supercritical drying condition are identical with embodiment 6, and gained aeroge sample is further through 500 ℃ of roastings 5 hours, and making specific area is 117m
2G
-1Anatase nanometer crystal aeroge TiO
2Sample.Nitrobenzene photocatalysis experiment is with embodiment 1, and the photocatalytic degradation experimental result shows that the nitrobenzene clearance is 97% on the sample that embodiment 10 synthesizes after 40 minutes.
Claims (7)
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