CN100450925C - Process for synthesizing mesoporous TiO2 using phosphotungstic acid as template agent - Google Patents
Process for synthesizing mesoporous TiO2 using phosphotungstic acid as template agent Download PDFInfo
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- CN100450925C CN100450925C CNB2006101140917A CN200610114091A CN100450925C CN 100450925 C CN100450925 C CN 100450925C CN B2006101140917 A CNB2006101140917 A CN B2006101140917A CN 200610114091 A CN200610114091 A CN 200610114091A CN 100450925 C CN100450925 C CN 100450925C
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- wolframic acid
- phosphotungstic acid
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Abstract
The process of synthesizing mesoporous TiO2 with phosphotungstic acid as template agent relates to process of synthesizing mesoporous molecular sieve and realizing material doping modification with solid acid template agent and belongs to the field of inorganic porous material synthesizing technology. The mesoporous TiO2 is synthesized through dissolving tetrabutyl titanate in anhydrous alcohol and adding water solution of phosphotungstic acid via stirring; taking the mixture, rotation evaporating and washing; vacuum drying and roasting at 500deg.C for 3 hr. The present invention utilizes the Keggin structure of phosphotungstic acid to form hydrogen bond between the water molecule and phosphotungstic acid molecule and to serve as template agent so as to synthesize the mesoporous material and modify TiO2 simultaneously. The mesoporous TiO2 has great specific surface area, homogeneous pore size, ordered structure and excellent stability.
Description
Technical field
The present invention relates to a kind of phospho-wolframic acid is the synthesising mesoporous TiO of template
2Method, relate in particular to the method that the synthesising mesoporous molecular sieve of a kind of solid acid template is realized synchronously material doped modification, belong to inorganic porous material synthetic method technical field
Technical background
Adopt the synthesising mesoporous TiO of improved sol-gel method since nineteen ninety-five
2Since, mesoporous TiO
2Owing to have bigger specific surface area and pore volume, regulatable aperture size and modifiable surface properties etc., be subjected to comprising ambit researchists' such as being engaged in heterogeneous catalyst, fractionation by adsorption and high inorganic materials extensive attention.
At synthesising mesoporous TiO
2In the process of molecular sieve, adopt organic formwork agents such as amine, superpolymer, positively charged ion or anion surfactant as pore-creating agent, building-up process last must high-temperature roasting or adopt solvent-extracted method that organic formwork agent is removed more.The method of direct roasting can cause the contraction of inorganic skeleton and the damage of ordered structure, and solvent extration can not be removed the template in the mesopore molecular sieve fully, is difficult to simultaneously guarantee that the cleaning of solvent is nontoxic.Therefore, press for the new synthesising mesoporous TiO of method of development
2Molecular sieve.
Ideal synthetic method method should have following characteristics: (1) is easy and simple to handle, and adopting nontoxic, pollution-free material is reaction medium; (2) meso-hole structure and the surface property of maintenance mesopore molecular sieve are easy to doping vario-property; (3) with low cost.
Phospho-wolframic acid is as a kind of solid strong acid, because its strongly-acid, satisfactory stability, advantage such as cheap are most widely used in solid acid.Relevant investigator adopts the method for dipping that phospho-wolframic acid is carried on TiO
2Catalytic activity has been improved on the molecular sieve surface, but material is stable inadequately, and solid acid easily comes off, and the load homogeneity has much room for improvement.Above method of modifying is at TiO
2An independent operation steps after synthetic needs the regular hour.
Summary of the invention
The present invention is intended to propose a kind of easy, cheap, effective means at synthesising mesoporous TiO
2The time realized the modification processing, with the maximum saving operating time.Material after the modification has good application prospects in fields such as photoelectric device, transmitter, heterogeneous catalysts.
The mesoporous TiO that the present invention proposes
2The synthetic method of molecular sieve is a template with the phospho-wolframic acid, utilizes these characteristics that form hydrogen bond between phospho-wolframic acid Keggin structure and water molecules, has realized material doped modification in the time of synthesize meso-porous material.
A kind of phospho-wolframic acid is the synthesising mesoporous TiO of template
2Method, its step is as follows:
(1) tetrabutyl titanate is dissolved in dehydrated alcohol, after mixing, adds the aqueous solution of phospho-wolframic acid, stir 3h;
(2) add deionized water, continue to stir 2h;
(3) mixture is taken out, rotary evaporation is with deionized water, absolute ethanol washing;
(4) after the vacuum-drying, 500 ℃ of roastings promptly obtain described mesoporous TiO
2
In the above-mentioned synthetic method, the mass ratio of tetrabutyl titanate and dehydrated alcohol is 1: 7; The phosphotungstic acid aqueous solution concentration of using is 0.01M～0.20M; The volume ratio of phospho-wolframic acid volume and deionized water is 0.96: 10; Roasting time is 3 hours.
In the above-mentioned synthetic method, the template phospho-wolframic acid of use need not to remove, and has realized doping vario-property in synthetic materials.
The present invention is a template with the phospho-wolframic acid, has synthesized that specific surface area is big, the aperture is even, structurally ordered, the mesoporous TiO with satisfactory stability
2The characteristics of this method are to utilize the characteristics of phospho-wolframic acid Keggin structure, at water molecules and the intermolecular formation hydrogen bond of phospho-wolframic acid, have played the effect of template, and the phospho-wolframic acid of introducing need not to remove, and have realized TiO in the time of synthesize meso-porous material
2Doping vario-property.Simplified operating process, with low cost, simple and easy to do.This method can the success phospho-wolframic acid is introduced TiO
2In the structure, the mesopore molecular sieve that the mesopore molecular sieve of preparation obtains than traditional organic formwork agent method has higher specific surface area and uniform more pore size distribution.The present invention can be used for various mesoporous TiO
2Synthetic and the modification of molecular sieve is handled.
Description of drawings
The TiO of Fig. 1 for obtaining by embodiment 4
2The XRD result schematic diagram.
The TiO of Fig. 2 for obtaining by embodiment 4
2The FTIR result schematic diagram.
The TiO of Fig. 3 for obtaining by embodiment 4
2SEM figure (1).
The TiO of Fig. 4 for obtaining by embodiment 4
2SEM figure (2).
Embodiment
Embodiment 1:
After 3.6g tetrabutyl titanate and dehydrated alcohol mixed by mass ratio at 1: 7, stir that to add the 0.48ml phospho-wolframic acid down water-soluble, concentration is 0.01M, stirs Dropwise 5 ml deionized water behind the 3h, continues to stir 2h; Take out the back rotary evaporation, with deionized water, absolute ethanol washing repeatedly, after the drying, 500 ℃ of roasting 3h promptly obtain described mesoporous TiO
2
Embodiment 2:
After 3.6g tetrabutyl titanate and dehydrated alcohol mixed by mass ratio at 1: 7, stir that to add the 0.48ml phospho-wolframic acid down water-soluble, concentration is 0.05M, stirs Dropwise 5 ml deionized water behind the 3h, continues to stir 2h; Take out the back rotary evaporation, with deionized water, absolute ethanol washing repeatedly, after the drying, 500 ℃ of roasting 3h promptly obtain described mesoporous TiO
2
Embodiment 3:
After 3.6g tetrabutyl titanate and dehydrated alcohol mixed by mass ratio at 1: 7, stir that to add the 0.48ml phospho-wolframic acid down water-soluble, concentration is 0.1M, stirs Dropwise 5 ml deionized water behind the 3h, continues to stir 2h; Take out the back rotary evaporation, with deionized water, absolute ethanol washing repeatedly, after the drying, 500 ℃ of roasting 3h promptly obtain described mesoporous TiO
2
Embodiment 4:
After 3.6g tetrabutyl titanate and dehydrated alcohol mixed by mass ratio at 1: 7, stir that to add the 0.48ml phospho-wolframic acid down water-soluble, concentration is 0.15M, stirs Dropwise 5 ml deionized water behind the 3h, continues to stir 2h; Take out the back rotary evaporation, with deionized water, absolute ethanol washing repeatedly, after the drying, 500 ℃ of roasting 3h promptly obtain described mesoporous TiO
2
Embodiment 5:
After 3.6g tetrabutyl titanate and dehydrated alcohol mixed by mass ratio at 1: 7, stir that to add the 0.48ml phospho-wolframic acid down water-soluble, concentration is 0.2M, stirs Dropwise 5 ml deionized water behind the 3h, continues to stir 2h; Take out the back rotary evaporation, with deionized water, absolute ethanol washing repeatedly, after the drying, 500 ℃ of roasting 3h promptly obtain described mesoporous TiO
2
The mesoporous TiO that obtains by above embodiment
2The molecular sieve specific surface area, pore volume and mean pore size are as shown in table 1, and table 1 is synthetic TiO under the different phosphate wolframic acid concentration
2The BET result of powder is by regulation and control phospho-wolframic acid concentration, the TiO that can obtain high-specific surface area, have even pore structure
2Material.The TiO that obtains with embodiment 4
2Be example, as follows to its analysis and characterization result who carries out: XRD result shows that the synthetic material is an anatase octahedrite, detects the characteristic peak less than phospho-wolframic acid, as shown in Figure 1 (the TiO of Fig. 1 for being obtained by embodiment 4
2The XRD result schematic diagram.); The FTIR analytical results detects the characteristic peak less than phospho-wolframic acid, sees Fig. 2 (TiO of Fig. 2 for being obtained by embodiment 4
2The FTIR result schematic diagram.), so TiO
2Material surface does not have the existence of phospho-wolframic acid; Table 2 is TiO
2The XPS characterization result, the visible synthetic TiO of institute
2The mol ratio of middle P and W and the coupling of the mol ratio in the phospho-wolframic acid; Therefore, the phospho-wolframic acid success is incorporated into TiO
2In the structure, in synthetic materials, phospho-wolframic acid is introduced TiO
2, realized doping vario-property.Fig. 3 and Fig. 4 are the TiO that is obtained by embodiment 4
2SEM result, be same sample, different part obtain than clear photograph, be the spheroidal particle of size about 500nm, even structure.
Synthetic TiO under the table 1 different phosphate wolframic acid concentration
2The BET result of powder
| Phospho-wolframic acid concentration, M | Specific surface area, m 2/g | Pore volume, cm 1/g | Mean pore size, nm |
| 0.01 | 30 | 0.109 | 14.4 |
| 0.05 | 97 | 0.136 | 5.6 |
| 0.1 | 93 | 0.135 | 5.8 |
| 0.15 | 150 | 0.178 | 4.8 |
| 0.2 | 152 | 0.137 | 3.6 |
The TiO that table 2 is obtained by embodiment 4
2The XRF analysis result of material
| Element | Mass ratio, % |
| 0 | 45.8554 |
| Ti | 45.0150 |
| W | 8.8695 |
| P | 0.1268 |
| Other | 0.1333 |
Claims (2)
1, a kind of phospho-wolframic acid is the synthesising mesoporous TiO of template
2Method, it is characterized in that this method may further comprise the steps:
(1) is to be dissolved in dehydrated alcohol at 1: 7 with tetrabutyl titanate by the mass ratio of tetrabutyl titanate and dehydrated alcohol, after mixing, adds the aqueous solution of phospho-wolframic acid, stirred 3 hours;
(2) add deionized water, continue to stir 2 hours; The aqueous solution volume ratio of deionized water and described phospho-wolframic acid is 10: 0.96;
(3) step (2) mixture is taken out, rotary evaporation is with deionized water, absolute ethanol washing;
(4) material after step (3) washing is carried out vacuum-drying, 500 ℃ of roastings are 3 hours then, promptly obtain described mesoporous TiO
2
2, a kind of phospho-wolframic acid according to claim 1 is the synthesising mesoporous TiO of template
2Method, it is characterized in that the concentration of aqueous solution of described phospho-wolframic acid is 0.01M～0.20M.
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2444550C2 (en) * | 2009-05-04 | 2012-03-10 | Государственное образовательное учреждение высшего профессионального образования "Челябинский государственный педагогический университет" ГОУ ВПО "ЧГПУ" | Method of producing titanium dioxide |
| CN102897832B (en) * | 2011-07-26 | 2014-12-10 | 中国科学院长春应用化学研究所 | Preparation methods of two types of titanium dioxide, and water system super-capacitor |
| CN110028075B (en) * | 2019-05-09 | 2022-09-09 | 东北石油大学 | Method for preparing walnut shell morphology mesoporous material by regulating and controlling rice hulls through anions |
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| 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 |
| CN1636879A (en) * | 2004-12-02 | 2005-07-13 | 攀钢集团攀枝花钢铁研究院 | Prepn process of nanometer mesoporous TiO2 powder |
| CN1686821A (en) * | 2005-05-23 | 2005-10-26 | 北京工业大学 | Method for preparing medium pore molecular sieve of titanium dioxide |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN1636879A (en) * | 2004-12-02 | 2005-07-13 | 攀钢集团攀枝花钢铁研究院 | Prepn process of nanometer mesoporous TiO2 powder |
| CN1686821A (en) * | 2005-05-23 | 2005-10-26 | 北京工业大学 | Method for preparing medium pore molecular sieve of titanium dioxide |
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| H3PW12O40/TiO2催化合成苯甲醛1，2－丙二醇缩醛. 许招会，廖维林，王生.日用化学工业，第35卷第6期. 2005 |
| H3PW12O40/TiO2催化合成苯甲醛1，2－丙二醇缩醛. 许招会，廖维林，王生.日用化学工业，第35卷第6期. 2005 * |
| 复合模板剂下有序介孔TiO2的制备研究. 王金忠，赵岩，张彩碚.物理化学学报，第19卷第3期. 2003 |
| 复合模板剂下有序介孔TiO2的制备研究. 王金忠，赵岩，张彩碚.物理化学学报，第19卷第3期. 2003 * |
| 磷钨系杂多酸复合TiO2纳米粒子的制备及光催化特性. 刘战辉，张宇，李昌安，顾宁，付德刚.江苏化工，第32卷第3期. 2004 |
| 磷钨系杂多酸复合TiO2纳米粒子的制备及光催化特性. 刘战辉，张宇，李昌安，顾宁，付德刚.江苏化工，第32卷第3期. 2004 * |
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| 锐钛型介孔纳米二氧化钛粉体的制备与表征. 戴亚堂，陶宁，童云，涂铭旌.四川大学学报，第38卷第2期. 2006 * |
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