CN101830503A - Method for preparing novel porous honeycomb mesoporous titanium dioxide material - Google Patents
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- CN101830503A CN101830503A CN 201010145271 CN201010145271A CN101830503A CN 101830503 A CN101830503 A CN 101830503A CN 201010145271 CN201010145271 CN 201010145271 CN 201010145271 A CN201010145271 A CN 201010145271A CN 101830503 A CN101830503 A CN 101830503A
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Abstract
The invention discloses a method for preparing a novel porous honeycomb mesoporous titanium dioxide material, which relates to a method for preparing a mesoporous titanium dioxide material, and belongs to the technical field of a titanium dioxide photocatalyst. Organic acid and alcohol and an inorganic titanium source of C2-C9, and organic acid and an organic titanium source of C2-C9 are used as the raw materials in the method. The method comprises the following steps: uniformly mixing the organic acid and the titanium source in the molar ratio of 1-10:1, reacting for 0.5-1.0h at the temperature of 10 DEG C-80 DEG C, and evaporating the solvent to obtain a honeycomb puffing solid; roasting for 1-5h at the temperature of 200-700 DEG C to obtain the porous honeycomb mesoporous titanium dioxide material. The invention has the advantages of easily obtained raw materials, simple preparation method, short preparation time, and no need of adding templates. The obtained mesoporous titanium dioxide has both visible pores and the mesopores, the distribution of pore diameters is narrow, the micropore diameter is 20-30nm, and the specific area is 90-160m<2>/g. The mesoporous titanium dioxide material has certain hardness, is easy to separate from liquid phase, can achieve good separation effect by decantation, has high photocatalytic activity, and is especially suitable for the fields of photocatalysis.
Description
Technical field
The invention belongs to the titanium dioxide optical catalyst technical field, be specifically related to a kind of preparation method of porous honeycomb mesoporous titanium dioxide, especially make visible hole and mesoporous simultaneous a kind of preparation method.
Technical background
Nano titanium oxide is a kind of nontoxic semi-conductor, under the irradiation of UV-light, can produce light induced electron and photohole, light induced electron has strong reducing power, photohole has strong oxidation capacity, light induced electron and photohole can decompose, purify as inorganic and organic waste waters such as ammonia, amine, phenols, and bacterium is had killing action.Disclose with the objectionable impurities in the titanium dioxide decomposition refuse as JP2-9850B.Nano titanium oxide also has superior corrosion resistance and fast light corrodibility, has a wide range of applications at aspects such as photochemical catalysis, photodegradation, environmental treatment.
The photocatalytic activity of nano titanium oxide has been well-known, but reclaims difficulty, is easy to problem such as loss and makes it fail to be used widely at aspects such as photochemical catalytic oxidation, wastewater treatments always because of it.In view of mesoporous material had both had nanostructure, have certain volume again, be difficult for running off, be easy to advantages such as recovery, decades the research of mesoporous TiO 2 as photocatalyst and support of the catalyst is received much concern always recently.
At present, the general employing template of preparation mesoporous TiO 2, used template mainly contain the silicon oxide of the polyvinylpyrrolidone reported among cetyl trimethylammonium bromide, nonionogenic tenside such as the patent CN1322676 of cats product such as Journal of Inorganic Materials 2009 (5) 902-908 pages or leaves report and mineral crystal template such as patent CN1287878 report and anion surfactant etc.Most of template are removed comparatively difficulty.Prepare mesoporous TiO 2 etc. as disclosed silicon oxide in the silicon titanium mixture removal among the patent CN1287878 with alkali solution technique.
Summary of the invention
Main purpose of the present invention provides a kind of preparation method of mesoporous TiO 2 of cellular visible pore structure, the visible hole of gained mesoporous TiO 2 and mesoporous and deposit, and pore size distribution is narrower, and micropore size is 20～30nm, and specific surface area is 90～160m
2/ g, the block volume adjustable size that makes and certain rigidity is arranged is easy to and liquid phase separation, and decantation can reach separating effect preferably, and catalyzer is difficult for running off, and reclaims easily, the photocatalytic activity height.
The objective of the invention is to be to realize by following technical scheme:
A kind of preparation method of novel porous honeycomb mesoporous titanium dioxide material comprises following preparation process:
(1) join in reactor that water distilling apparatus be housed by 1: 1 molar ratio pure and mild organic acid or add template simultaneously, template is 3～6: 100 with titanium source quality ratio, mixes;
(2) organic acid is joined in the reactor that water distilling apparatus is housed or add template simultaneously, template is 3～6: 100 with titanium source quality ratio, mixes;
(3) under room temperature or cooling bath condition, inorganic ti sources slowly is added drop-wise in the solution of step (1) gained, the organic titanium source slowly is added drop-wise in the solution of step (2) gained and obtains oyster or light yellowish brown clear solution; Titanium source and organic acid mol ratio are 1: 1～10;
(4) with after the reaction of step (3) gained solution stirring, heating up slowly to steam desolventizes, and holding temperature makes and keeps slight boiling condition until evaporate to dryness, and temperature is lower than 120 ℃, obtains the bulk solid of cellular white titanium dioxide;
(5) with the bulk solid of the cellular white titanium dioxide of step (4) gained in 200～700 ℃ of following roastings of temperature, obtain porous honeycomb mesoporous titanium dioxide material.
The preparation method of described a kind of novel porous honeycomb mesoporous titanium dioxide material, described porous honeycomb mesoporous titanium dioxide material outward appearance such as cellular bulk, the block volume adjustable size, the macropore naked eyes as seen, hole wall is thinner, porosity is big, as seen hole and mesoporous and deposit, pore size distribution is narrower, and micropore size is 20～30nm, and specific surface area is 90～160m
2/ g.
The preparation method of described a kind of novel porous honeycomb mesoporous titanium dioxide material adds template or does not add the titanic oxide material that template makes meso-hole structure.
The preparation method of described a kind of novel porous honeycomb mesoporous titanium dioxide material, described inorganic ti sources is titanium tetrachloride, titanyl sulfate, the organic titanium source is tetraethyl titanate, tetrabutyl titanate.
The preparation method of described a kind of novel porous honeycomb mesoporous titanium dioxide material, described alcohol is one or more pure mixtures of ethanol, ethylene glycol, propyl alcohol, propylene glycol, glycerol, butanols or butyleneglycol, and described organic acid is acetate, propionic acid, oxalic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad or one or more sour mixtures of n-nonanoic acid.
The preparation method of described a kind of novel porous honeycomb mesoporous titanium dioxide material, the dropping time of described step (3) is 0.5～1.0h.
The preparation method of described a kind of novel porous honeycomb mesoporous titanium dioxide material, the reaction times of described step (4) is 0.5～1.0h.
The preparation method of described a kind of novel porous honeycomb mesoporous titanium dioxide material, the roasting time of described step (5) is 1～5h.
The present invention compared with prior art has following advantage:
1. the porous honeycomb mesoporous titanium dioxide solid of the present invention preparation, the structure that has visible hole and mesoporous while and deposit.
2. the present invention can make the titanium dioxide of meso-hole structure under the condition that does not add template, and the photochemical catalysis effect is remarkable.
3. preparation method of the present invention can be anhydrous condition, has reduced three-waste pollution.
4. preparation method of the present invention is simple, easy and simple to handle, the reaction conditions gentleness, and preparation time is short, is easy to apply.
5. the cellular porous mesoporous TiO 2 solid volume adjustable size of the present invention preparation, have certain degree of hardness, not easily broken, solid-liquid separation is easy, can effectively avoid problems such as catalyst loss, recovery difficulty, have wide practical use in fields such as photochemical catalytic oxidation, wastewater treatments.
Description of drawings
Fig. 1 is that embodiments of the invention 1 and example 2 photocatalysts are to the degradation rate of methylene blue and the relation curve of degradation time.
Embodiment
Embodiment 1
Do not add template and prepare porous honeycomb mesoporous titanium dioxide:
Add 21mL ethanol and 22mL Glacial acetic acid in the reaction vessel that water distilling apparatus is housed, stirring is clear solution.Slowly drip the 10mL titanium tetrachloride under the room temperature in above-mentioned clear solution, stir simultaneously, about 1h adds.Obtain the oyster clear solution after adding, heating up slowly to steam behind the stirring 0.5h desolventizes, and reclaims hydrochloric acid simultaneously.Steaming desolventizes and can be observed Tyndall phenomenon when thick.Continue elevated temperature to beginning bubbling, holding temperature makes and keeps the bubbling state until evaporate to dryness, and temperature is lower than 120 ℃, gets the bulk solid of white titanium dioxide of cellular visible pore structure, and macropore diameter is about 1-3mm, and this moment, solid was more crisp, was about 11g.Obtain the bulk solid of white mesoporous TiO 2 of cellular visible pore structure behind 400 ℃ of roasting 3h, macropore diameter is 1-3mm, and mesoporous aperture is about 23nm, and this moment, solid had certain rigidity, was about 7g, got sample A.
Embodiment 2
Add template and prepare porous honeycomb mesoporous titanium dioxide:
Add 1g cetyl trimethylammonium bromide, 21mL ethanol and 22mL Glacial acetic acid in the reaction vessel that water distilling apparatus is housed, stirring is clear solution.Slowly drip the 10mL titanium tetrachloride under the room temperature in above-mentioned clear solution, stir simultaneously, about 1h adds.Obtain the light yellowish brown clear solution after adding, heating up slowly to steam behind the stirring 0.5h desolventizes, and reclaims hydrochloric acid simultaneously.Steaming desolventizes and can be observed Tyndall phenomenon when thick.Continue elevated temperature to beginning bubbling, holding temperature makes and keeps the bubbling state until evaporate to dryness, and temperature is lower than 120 ℃, gets the bulk solid of white titanium dioxide of cellular visible pore structure, and macropore diameter is about 1-3mm, and this moment, solid was more crisp, was about 12g.Obtain the bulk solid of white mesoporous TiO 2 of cellular visible pore structure behind 500 ℃ of roasting 2h, macropore diameter is about 1-3mm, and mesoporous aperture is about 27nm, and this moment, solid had certain rigidity, was about 7g, got sample B.
Take by weighing resulting sample A of 0.25g and B respectively, to have cooling water jecket, the ultraviolet lamp of power 25W is done light source, and degraded 50mL, starting point concentration are the methylene blue solution of 20mg/L.The silica tube that methylene blue solution and photocatalyst are housed is apart from light source 20cm.
Embodiment 3
Do not add template and prepare porous honeycomb mesoporous titanium dioxide:
Add the 26mL Glacial acetic acid in the reaction vessel that water distilling apparatus is housed, slowly drip the 20mL tetrabutyl titanate under the water-bath cooling conditions in aforesaid liquid, stir simultaneously, about 1h adds.Obtain the oyster clear solution after adding, heating up slowly to steam behind the stirring 1.0h desolventizes.Steaming desolventizes and can be observed Tyndall phenomenon when thick.Continue elevated temperature to beginning bubbling, holding temperature makes and keeps the bubbling state until evaporate to dryness, and temperature is lower than 120 ℃, gets the bulk solid of white titanium dioxide of cellular visible pore structure, and macropore diameter is about 1-3mm, and this moment, solid was more crisp, was about 9g.Obtain the bulk solid of white mesoporous TiO 2 of cellular visible pore structure behind 300 ℃ of roasting 4h, macropore diameter is 1-3mm, and mesoporous aperture is about 24nm, and this moment, solid had certain rigidity, was about 4g.
Embodiment 4
Add template and prepare porous honeycomb mesoporous titanium dioxide:
Add 1g cetyl trimethylammonium bromide, 26mL Glacial acetic acid in the reaction vessel that water distilling apparatus is housed, stirring is clear solution.Slowly drip the 20mL tetrabutyl titanate under the water-bath cooling conditions in above-mentioned clear solution, stir simultaneously, about 1h adds.Obtain the light yellowish brown clear solution after adding, heating up slowly to steam behind the stirring 0.5h desolventizes.Steaming desolventizes and can be observed Tyndall phenomenon when thick.Continue elevated temperature to beginning bubbling, holding temperature makes and keeps the bubbling state until evaporate to dryness, and temperature is lower than 120 ℃, gets the bulk solid of white titanium dioxide of cellular visible pore structure, and macropore diameter is about 1-3mm, and this moment, solid was more crisp, was about 10g.Obtain the bulk solid of white mesoporous TiO 2 of cellular visible pore structure behind 600 ℃ of roasting 1h, macropore diameter is about 1-3mm, and mesoporous aperture is about 26nm, and this moment, solid had certain rigidity, was about 4g.
Claims (8)
1. the preparation method of a novel porous honeycomb mesoporous titanium dioxide material is characterized in that comprising following preparation process:
(1) join in reactor that water distilling apparatus be housed by 1: 1 molar ratio pure and mild organic acid or add template simultaneously, template is 3～6: 100 with titanium source quality ratio, mixes;
(2) organic acid is joined in the reactor that water distilling apparatus is housed or add template simultaneously, template is 3～6: 100 with titanium source quality ratio, mixes;
(3) under room temperature or cooling bath condition, inorganic ti sources slowly is added drop-wise in the solution of step (1) gained, the organic titanium source slowly is added drop-wise in the solution of step (2) gained and obtains oyster or light yellowish brown clear solution; Titanium source and organic acid mol ratio are 1: 1～10;
(4) with after the reaction of step (3) gained solution stirring, heating up slowly to steam desolventizes, and holding temperature makes and keeps slight boiling condition until evaporate to dryness, and temperature is lower than 120 ℃, obtains the bulk solid of cellular white titanium dioxide;
(5) with the bulk solid of the cellular white titanium dioxide of step (4) gained in 200～700 ℃ of following roastings of temperature, obtain porous honeycomb mesoporous titanium dioxide material.
2. the preparation method of a kind of novel porous honeycomb mesoporous titanium dioxide material according to claim 1, it is characterized in that: described porous honeycomb mesoporous titanium dioxide material outward appearance such as cellular bulk, the block volume adjustable size, the macropore naked eyes as seen, hole wall is thinner, porosity is big, as seen hole and mesoporous and deposit, pore size distribution is narrower, and micropore size is 20～30nm, and specific surface area is 90～160m
2/ g.
3. the preparation method of a kind of novel porous honeycomb mesoporous titanium dioxide material according to claim 1 is characterized in that: add template or do not add the titanic oxide material that template makes meso-hole structure.
4. the preparation method of a kind of novel porous honeycomb mesoporous titanium dioxide material according to claim 1, it is characterized in that: described inorganic ti sources is titanium tetrachloride, titanyl sulfate, the organic titanium source is tetraethyl titanate, tetrabutyl titanate.
5. the preparation method of a kind of novel porous honeycomb mesoporous titanium dioxide material according to claim 1, it is characterized in that: described alcohol is one or more pure mixtures of ethanol, ethylene glycol, propyl alcohol, propylene glycol, glycerol, butanols or butyleneglycol, and described organic acid is acetate, propionic acid, oxalic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad or one or more sour mixtures of n-nonanoic acid.
6. the preparation method of a kind of novel porous honeycomb mesoporous titanium dioxide material according to claim 1, it is characterized in that: the dropping time of described step (3) is 0.5～1.0h.
7. the preparation method of a kind of novel porous honeycomb mesoporous titanium dioxide material according to claim 1, it is characterized in that: the reaction times of described step (4) is 0.5～1.0h.
8. the preparation method of a kind of novel porous honeycomb mesoporous titanium dioxide material according to claim 1, it is characterized in that: the roasting time of described step (5) is 1～5h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225783A (en) * | 2011-05-30 | 2011-10-26 | 南京钛威科技有限公司 | Preparation method of macroporous titanium oxide or precursor of macroporous titanium oxide |
| CN103611480A (en) * | 2013-12-06 | 2014-03-05 | 河南师范大学 | Method for preparing homogenesis yolk-shell structure titanium dioxide microsphere |
| CN105126797A (en) * | 2015-07-21 | 2015-12-09 | 天津霍普环保科技有限公司 | Honeycomb ceramic-supported nano titanium dioxide photo-catalyst and preparation method of same |
| CN107903675A (en) * | 2017-12-21 | 2018-04-13 | 金华联创塑粉科技有限公司 | A kind of low VOC environment-friendly type coatings and preparation method thereof |
| CN109052467A (en) * | 2018-08-29 | 2018-12-21 | 常州大学 | A kind of honeycomb TiO with three-dimensional perforation stomata characteristics2The synthetic method of lamella |
| CN110079187A (en) * | 2019-04-08 | 2019-08-02 | 沈阳化工大学 | A kind of aqueous dual preparation method except methanal paint |
| CN111620362A (en) * | 2020-04-24 | 2020-09-04 | 广西科学院 | Microwave preparation method of mesoporous holmium oxide powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186774A (en) * | 1998-01-14 | 1998-07-08 | 中国科学院固体物理研究所 | Large mass TiO2 mesohole solid and preparing method |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186774A (en) * | 1998-01-14 | 1998-07-08 | 中国科学院固体物理研究所 | Large mass TiO2 mesohole solid and preparing method |
Non-Patent Citations (1)
| Title |
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| 《无机盐工业》 20070531 乔秀丽等 以四氯化钛为原料溶剂热法合成介孔二氧化钛 第39卷, 第5期 2 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225783A (en) * | 2011-05-30 | 2011-10-26 | 南京钛威科技有限公司 | Preparation method of macroporous titanium oxide or precursor of macroporous titanium oxide |
| CN102225783B (en) * | 2011-05-30 | 2013-06-26 | 南京钛威科技有限公司 | Preparation method of macroporous titanium oxide or precursor of macroporous titanium oxide |
| CN103611480A (en) * | 2013-12-06 | 2014-03-05 | 河南师范大学 | Method for preparing homogenesis yolk-shell structure titanium dioxide microsphere |
| CN103611480B (en) * | 2013-12-06 | 2015-05-13 | 河南师范大学 | Method for preparing homogenesis yolk-shell structure titanium dioxide microsphere |
| CN105126797A (en) * | 2015-07-21 | 2015-12-09 | 天津霍普环保科技有限公司 | Honeycomb ceramic-supported nano titanium dioxide photo-catalyst and preparation method of same |
| CN107903675A (en) * | 2017-12-21 | 2018-04-13 | 金华联创塑粉科技有限公司 | A kind of low VOC environment-friendly type coatings and preparation method thereof |
| CN109052467A (en) * | 2018-08-29 | 2018-12-21 | 常州大学 | A kind of honeycomb TiO with three-dimensional perforation stomata characteristics2The synthetic method of lamella |
| CN110079187A (en) * | 2019-04-08 | 2019-08-02 | 沈阳化工大学 | A kind of aqueous dual preparation method except methanal paint |
| CN110079187B (en) * | 2019-04-08 | 2021-08-06 | 沈阳化工大学 | Preparation method of water-based double formaldehyde-removing coating |
| CN111620362A (en) * | 2020-04-24 | 2020-09-04 | 广西科学院 | Microwave preparation method of mesoporous holmium oxide powder |
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