CN1686821A - Method for preparing medium pore molecular sieve of titanium dioxide - Google Patents
Method for preparing medium pore molecular sieve of titanium dioxide Download PDFInfo
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- CN1686821A CN1686821A CN 200510070879 CN200510070879A CN1686821A CN 1686821 A CN1686821 A CN 1686821A CN 200510070879 CN200510070879 CN 200510070879 CN 200510070879 A CN200510070879 A CN 200510070879A CN 1686821 A CN1686821 A CN 1686821A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000011148 porous material Substances 0.000 title claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000000499 gel Substances 0.000 claims description 26
- 239000008240 homogeneous mixture Substances 0.000 claims description 16
- 229960004418 trolamine Drugs 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000005345 coagulation Methods 0.000 claims description 5
- 230000015271 coagulation Effects 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 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 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 4
- 235000019441 ethanol Nutrition 0.000 abstract 2
- 235000011187 glycerol Nutrition 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
The method for preparing nano titanium dioxide metaporous material includes the following steps: mixing titanium source and triethanolamine at room temp., uniformly stirring them, drop-adding one of water, propanetriol, glycol and ethyl alcohol as solvent, regulating pH value and making it be 7-9; drying for 2-48 hr, at 25 deg.C-180 deg.C to form homogeneous gel, making crystallization for 12-96 hr, at 25-180 deg.C in a closed reactor, heating to 300-800 deg.C, heat-insulating for 10-20 hr, or using alcohol solution to extract for 24-72 hr, and grinding so as to obtain the titanium dioxide metaporous molecular sieve.
Description
Technical field
The present invention relates to a kind of preparation method of titanic oxide material, particularly relate to a kind of preparation method of nano titanium oxide mesoporous material.
Background technology
Porous material is widely used in fields such as catalytic separation.Mesopore molecular sieve is compared with the micro porous molecular sieve of classics, has bigger aperture and specific surface area.Meso-porous molecular sieve material provides favourable sterie configuration and has selected the type active centre for organic macromolecule participates in reaction as catalyzer or support of the catalyst, has the potential application advantage in refining of petroleum or fine chemistry industry industry.
Transition metal oxide has special nature, and the transition metal oxide of various meso-hole structures obtains unprecedented concern in recent years.Titanium dioxide is a kind of nontoxic semi-conductor, under the irradiate light of UV, visible light wavelength, can produce photohole and light induced electron, and have good anti-corrosion, is having broad application prospects aspect photochemical catalysis, photodegradation, the environment protection.The preparation method of medium pore molecular sieve of titanium dioxide is existing at present a lot, used template comprises high-molecular block copolymer, cats product dodecyl trimethylammonium amine bromide, chain alkyl amine tensio-active agent or the like, synthetic in the alcoholic solution or the aqueous solution by the precipitator method, hydrothermal synthesis method, sol-gel processing etc.Must in building-up process, mostly adopt the different tensio-active agent of change to make template or change synthetic method and prepare mesopore molecular sieve, the common issue with following points that these methods exist:
1. tensio-active agent or organic molecule itself cost an arm and a leg.
2. most of tensio-active agents or organic molecule toxicity are bigger.
3. making complicated process of preparation influences the condition increase of reaction, and control building-up process difficulty strengthens.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of synthesis of nano medium pore molecular sieve of titanium dioxide method, its advantage is that synthesis technique is simple, with low cost, the titanium deoxide mesoporous molecular sieve modification for preparing is controlled, the duct controllable size, crystal particle diameter about 20nm, the photocatalytic activity height.
Be described in detail embodiment of the present invention below:
Using sol-gel processing, is template with the trolamine, and the titanium source of employing is a tetrabutyl titanate, and isopropyl titanate or titanium tetrachloride be the synthesis of titanium dioxide mesopore molecular sieve in the aqueous solution or in the organic solution.
The invention provides a kind of method for preparing medium pore molecular sieve of titanium dioxide, it is characterized in that, may further comprise the steps:
(1) at room temperature with the titanium source, it is tetrabutyl titanate, isopropyl titanate or titanium tetrachloride thrin are mixed with trolamine, one of back dropping water, glycerol, ethylene glycol, the ethanol of stirring is made solvent, wherein Ti in the titanium source and trolamine mol ratio are between 1: 0.2～1: 5, and one of Ti in the titanium source and water, glycerol, ethylene glycol, ethanol mol ratio is between 1: 4～1: 100;
(2) regulate pH value between 7～9, continue stirring and obtain a kind of homogeneous mixture;
2～48 hours after coagulations of (3) 25 ℃～180 ℃ above-mentioned homogeneous mixtures of drying form a kind of homogeneous phase gel, then gel are moved in the airtight withstand voltage reactor under 25 ℃～180 ℃ temperature crystallization 12～96 hours, obtain block gel;
(4) above-mentioned block gel is warming up to 300～800 ℃ through 1 ℃～10 ℃/min speed, be incubated 10～20 hours, form powder and be medium pore molecular sieve of titanium dioxide or, also obtain medium pore molecular sieve of titanium dioxide after the grinding with 24～72 hours above-mentioned block gels of alcoholic solution extraction.
Said titanium source and trolamine proportioning between 1: 0.2～1: 5, preferred 1: 1～1: 3; Titanium source and water or glycerol or ethylene glycol or ethanol proportioning were preferably 1: 10～1: 40 between 1: 4～1: 100.
The calcining of above-mentioned steps (4) can make titanium deoxide mesoporous molecular sieve modification be respectively Detitanium-ore-type by the crystal formation that the control maturing temperature is controlled the titanium dioxide skeleton, rutile-type, or the mixed crystal of anatase octahedrite and rutile-type.In temperature is that roasting obtains the anatase octahedrite phase below 450 ℃, and 450 ℃～700 ℃ roastings are mixed crystal, are the rutile phase more than 700 ℃.
The extracting process of above-mentioned steps (4) is deviate from template and is obtained mesopore molecular sieve, XRD result is shown as titanium dioxide nanocrystalline, its photochemical catalysis effect significantly improves in visible-range, its uv-absorbing rate is compared with the ordinary titanium dioxide powder and is obtained the results are shown in Figure 5, and what be used for photocatalytic degradation formaldehyde the results are shown in Figure 6.Following table is a photochemical catalysis experiment specimen in use inventory:
| Numbering | Title | The place of production | Rank | Remarks |
| ??1 | Titanium dioxide | Tianjin good fortune chemical reagent in morning factory | Analytical pure | |
| ??2 | Titanium dioxide | Germany GESSUGA company | Analytical pure | Model: P25 |
| ??3 | Medium pore molecular sieve of titanium dioxide | Self-control |
The outstanding feature of medium pore molecular sieve of titanium dioxide provided by the invention:
1, is template synthesis of titanium dioxide mesopore molecular sieve with the trolamine, greatly reduces the cost of preparation, make preparation technology simple.
2, the titanium deoxide mesoporous molecular sieve modification that obtains is controlled, the duct controllable size be the aperture between 5～25nm, crystal particle diameter is about 20nm.
3, the titanic oxide material photocatalytic activity that obtains improves.
Description of drawings
Fig. 1 is the XRD diffractogram of medium pore molecular sieve of titanium dioxide.
Fig. 2 is the graph of pore diameter distribution of medium pore molecular sieve of titanium dioxide.Wherein scheme the graph of pore diameter distribution that a is mean pore size 23.03741nm, figure b is the graph of pore diameter distribution of mean pore size 8.41103nm.
Fig. 3 is the XRD diffractogram of medium pore molecular sieve of titanium dioxide different crystal forms, and wherein scheming a is the anatase octahedrite phase, and figure b is that mixed crystal anatase octahedrite phase content is that 58.3% rutile phase content is 41.7%, and figure c is the rutile phase.
Fig. 4 is the sem photograph of medium pore molecular sieve of titanium dioxide.
Fig. 5 is the different titanium dioxide and the uv-absorbing rate comparison diagram of medium pore molecular sieve of titanium dioxide.
Fig. 6 is the different titanium dioxide and the comparison diagram as a result of medium pore molecular sieve of titanium dioxide photocatalytic degradation formaldehyde.
Embodiment
Following examples further specify embodiment and effect
Embodiment 1
At room temperature mix 12ml tetrabutyl titanate and 4.7ml trolamine, it is 8 that the back dropping 16ml water that stirs records pH value, continue to stir and obtain a kind of homogeneous mixture, 12 hours after coagulations of 100 ℃ of above-mentioned homogeneous mixtures of drying form a kind of homogeneous phase gel, then gel was moved in the reactor under 150 ℃ of temperature crystallization 12 hours, obtain block gel, again above-mentioned product is warming up to 600 ℃ calcining with 1 ℃/min speed after, be incubated 10 hours, grinding obtains white powder, its XRD diffractogram as shown in Figure 1, pore size distribution is shown in Fig. 2 a.
Embodiment 2
At room temperature mix 12ml tetrabutyl titanate and 4.7ml trolamine, it is 8 that the back dropping 16ml water that stirs records pH value, continue to stir and obtain a kind of homogeneous mixture, 12 hours after coagulations of 100 ℃ of above-mentioned homogeneous mixtures of drying form a kind of homogeneous phase gel, then gel was moved in the reactor under 150 ℃ of temperature crystallization 48 hours, and obtained block gel and be divided into three parts.Extracting 24 hours, 48 hours, 72 hours extraction liquids respectively with apparatus,Soxhlet's is ethanolic soln, and the block gel that obtains grinds the back powdered, wherein extracts the product pore size distribution that obtained in 24 hours shown in Fig. 2 b.
Embodiment 3
At room temperature mix 3.4ml tetrabutyl titanate and 6.7ml trolamine, it is 8 that the back dropping 18ml water that stirs records pH value, continue to stir and obtain a kind of homogeneous mixture, 2 hours after coagulations of 180 ℃ of above-mentioned homogeneous mixtures of drying form a kind of homogeneous phase gel, then gel is moved in the reactor under 180 ℃ of temperature crystallization 48 hours, and obtained block gel; Again above-mentioned product is warming up to 400 ℃ calcining with 5 ℃/min speed after, be incubated 10 hours, grind and obtain white powder.Its XRD diffractogram is shown in Fig. 3 a.
Embodiment 4
At room temperature mix 15ml isopropyl titanate and 1.33ml trolamine, the back that stirs drips 9ml water, the ammoniacal liquor of the 5ml/L for preparing is dropwise added regulate pH value to 9, continues to stir, and demixing obtains gel.25 ℃ of above-mentioned homogeneous mixtures of drying moved in the reactor under 90 ℃ of temperature crystallization 96 hours after 48 hours, obtain block gel; Again above-mentioned product is warming up to 600 ℃ calcining with 10 ℃/min speed after, be incubated 20 hours, grind and obtain pale yellow powder.Its XRD diffractogram is shown in Fig. 3 b.
Embodiment 5
At room temperature mix 4ml tetrabutyl titanate and 1.6ml trolamine, it is 8 that the back dropping 2.2ml ethylene glycol that stirs records pH value, continue to stir and obtain a kind of homogeneous mixture, 60 ℃ of above-mentioned homogeneous mixtures of drying formed gel after 10 hours, moved in the reactor under 25 ℃ of temperature crystallization then 24 hours, again above-mentioned product is warming up to 800 ℃ calcining with 1 ℃/min speed after, be incubated 10 hours, grind and obtain pale yellow powder.Its XRD diffractogram is shown in Fig. 3 c.
Embodiment 6
At room temperature mix 1.1ml titanium tetrachloride and 4ml trolamine, the back that stirs drips 23.3ml ethanol, the hydrochloric acid of the 5ml/L for preparing is dropwise added regulate pH value to 7, continues to stir, and demixing obtains gel.100 ℃ of above-mentioned homogeneous mixtures of drying moved in the reactor under 150 ℃ of temperature crystallization 12 hours after 12 hours, obtain block gel; Above-mentioned product is warming up to 300 ℃ calcining with 1 ℃/min speed after, be incubated 15 hours again, grind and obtain white powder, the big I of its crystal particle diameter is found out about 20nm by the scanning electron microscope picture of Fig. 4.
Embodiment 7
At room temperature mix 4ml tetrabutyl titanate and 1.6ml trolamine, it is 8 that the back dropping 3ml glycerol that stirs records pH value, continue to stir and obtain a kind of homogeneous mixture, 100 ℃ of above-mentioned homogeneous mixtures of drying formed gel after 12 hours, moved in the reactor under 150 ℃ of temperature crystallization then 48 hours, again above-mentioned product is warming up to 600 ℃ calcining with 1 ℃/min speed after, be incubated 10 hours, grinding obtains pale yellow powder, and its photochemical catalysis effect and ordinary titanium dioxide powder comparative result are seen Fig. 5, Fig. 6.
Claims (3)
1, a kind of method for preparing medium pore molecular sieve of titanium dioxide is characterized in that, may further comprise the steps:
(1) at room temperature with the titanium source, it is tetrabutyl titanate, isopropyl titanate or titanium tetrachloride thrin are mixed with trolamine, one of back dropping water, glycerol, ethylene glycol, the ethanol of stirring is made solvent, wherein Ti in the titanium source and trolamine mol ratio are between 1: 0.2～1: 5, and one of Ti in the titanium source and water, glycerol, ethylene glycol, ethanol mol ratio is between 1: 4～1: 100;
(2) regulate pH value between 7～9, continue stirring and obtain a kind of homogeneous mixture;
2～48 hours after coagulations of (3) 25 ℃～180 ℃ above-mentioned homogeneous mixtures of drying form a kind of homogeneous phase gel, then gel are moved in the airtight withstand voltage reactor under 25 ℃～180 ℃ temperature crystallization 12～96 hours, obtain block gel;
(4) above-mentioned block gel is warming up to 300～800 ℃ through 1 ℃～10 ℃/min speed, be incubated 10～20 hours, form powder and be medium pore molecular sieve of titanium dioxide or, also obtain medium pore molecular sieve of titanium dioxide after the grinding with 24～72 hours above-mentioned block gels of alcoholic solution extraction.
2, method for preparing medium pore molecular sieve of titanium dioxide according to claim 1 is characterized in that, titanium source and trolamine proportioning are 1: 1～1: 3.
3, method for preparing medium pore molecular sieve of titanium dioxide according to claim 1 is characterized in that, titanium source and water or glycerol or ethylene glycol or ethanol proportioning are 1: 10～1: 40.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100434178C (en) * | 2006-03-16 | 2008-11-19 | 上海师范大学 | Process for preparing titanium dioxide photo catalyst |
| CN100450925C (en) * | 2006-10-27 | 2009-01-14 | 清华大学 | Process for synthesizing mesoporous TiO2 using phosphotungstic acid as template agent |
| CN101279857B (en) * | 2007-04-06 | 2011-11-09 | 清华大学 | Preparation of mesoporous material |
| CN103113874A (en) * | 2013-02-06 | 2013-05-22 | 陕西科技大学 | Organic titanium crosslinking agent, and preparation method and application method thereof |
| TWI448432B (en) * | 2011-12-21 | 2014-08-11 | Univ Nat Cheng Kung | Mesoporous titania bead and method for preparing the same |
| TWI458685B (en) * | 2011-06-29 | 2014-11-01 | Univ Nat Chiao Tung | Titanium dioxide nanopowder and manufacturing method thereof |
| TWI467784B (en) * | 2011-12-21 | 2015-01-01 | Univ Nat Cheng Kung | Solar cell |
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| CN111957305A (en) * | 2020-08-11 | 2020-11-20 | 上海锐朗光电材料有限公司 | Titanium dioxide microsphere photocatalyst and preparation method thereof |
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| CN1057982C (en) * | 1998-01-14 | 2000-11-01 | 中国科学院固体物理研究所 | Large mass TiO2 mesohole solid and preparing method |
| CN1363520A (en) * | 2001-01-09 | 2002-08-14 | 攀枝花市永禄科技开发有限责任公司 | Process for preparing rutile crystal type nano TiO2 |
| CN1247462C (en) * | 2003-08-05 | 2006-03-29 | 拉萨绿能科技实业有限公司 | New process for preparing anatase type nano titanium dioxide |
| CN1261359C (en) * | 2004-12-02 | 2006-06-28 | 攀钢集团攀枝花钢铁研究院 | Prepn process of nanometer mesoporous TiO2 powder |
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- 2005-05-23 CN CNB2005100708798A patent/CN1325381C/en not_active Expired - Fee Related
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| CN100434178C (en) * | 2006-03-16 | 2008-11-19 | 上海师范大学 | Process for preparing titanium dioxide photo catalyst |
| CN100450925C (en) * | 2006-10-27 | 2009-01-14 | 清华大学 | Process for synthesizing mesoporous TiO2 using phosphotungstic acid as template agent |
| CN101279857B (en) * | 2007-04-06 | 2011-11-09 | 清华大学 | Preparation of mesoporous material |
| TWI458685B (en) * | 2011-06-29 | 2014-11-01 | Univ Nat Chiao Tung | Titanium dioxide nanopowder and manufacturing method thereof |
| TWI448432B (en) * | 2011-12-21 | 2014-08-11 | Univ Nat Cheng Kung | Mesoporous titania bead and method for preparing the same |
| TWI467784B (en) * | 2011-12-21 | 2015-01-01 | Univ Nat Cheng Kung | Solar cell |
| CN103113874A (en) * | 2013-02-06 | 2013-05-22 | 陕西科技大学 | Organic titanium crosslinking agent, and preparation method and application method thereof |
| CN109354061A (en) * | 2018-10-18 | 2019-02-19 | 九江学院 | A kind of preparation method of monodisperse ultra-small grain size titanium dioxide nanocrystalline |
| CN109331800A (en) * | 2018-11-16 | 2019-02-15 | 内蒙古工业大学 | A kind of nanoporous TiO prepared with citric acid2For the preparation method of the vanadium based denitration catalyst of carrier |
| CN109331800B (en) * | 2018-11-16 | 2021-03-26 | 内蒙古工业大学 | Nano porous TiO prepared from citric acid2Preparation method of vanadium-based denitration catalyst as carrier |
| CN111957305A (en) * | 2020-08-11 | 2020-11-20 | 上海锐朗光电材料有限公司 | Titanium dioxide microsphere photocatalyst and preparation method thereof |
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| CN1325381C (en) | 2007-07-11 |
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