CN101624183B - Method for synthesizing nano-porous zirconium phosphate by using hybridization of ionic liquid - Google Patents
Method for synthesizing nano-porous zirconium phosphate by using hybridization of ionic liquid Download PDFInfo
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- CN101624183B CN101624183B CN2009100550848A CN200910055084A CN101624183B CN 101624183 B CN101624183 B CN 101624183B CN 2009100550848 A CN2009100550848 A CN 2009100550848A CN 200910055084 A CN200910055084 A CN 200910055084A CN 101624183 B CN101624183 B CN 101624183B
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Abstract
The invention discloses a method for synthesizing nano-porous zirconium phosphate by using hybridization of ionic liquid, the method comprises the steps of preparing the ionic liquid and synthesizing the nano-porous zirconium phosphate, the synthesis of the nano-porous zirconium phosphate is to place the ionic liquid, ZrOCl2 and water with the weight ratio of 1.5-4.5:1.0-3.0:2.0 in a polytetrafluoroethylene reaction kettle, the reaction is carried out for 12-36h at the temperature of 80-120 DEG C, the temperature is is lowered to room temperature after the completion of the reaction, 28% ammonia water is dripped in products for regulating pH to 8-10, and the solid products are taken out, washed by using ethanol and water and vacuum-dried, thereby obtaining the white nano-porous zirconium phosphate. The method grafts the ionic liquid with basic functional groups in nano-material, thereby effectively improving the performance of the solid nano-material and greatly expanding the application range of the functional material; and the synthesized material has amino functional groups, thereby having a certain absorption performance to CO2 and other acidic gases.
Description
Technical field
The present invention relates to the porous material technical field, specifically a kind of method with the hybridization of ionic liquid synthesizing nano-porous zirconium phosphate.
Background technology
The zirconium phosphate compounds is a class multifunctional material that progressively grows up in recent years, and the ion-exchange performance that existing ion exchange resin is the same has the same shape of selecting of zeolite to adsorb and catalytic performance again.Higher thermostability and resistance to acids and bases are preferably arranged again simultaneously.This class material is with the insertion of its uniqueness and support performance and present vast potential for future development, have huge potential using value at numerous areas such as chemistry, optics, electronics, electromagnetism, materialogy, environmentalisms, thereby make this class mesoporous material become the domestic and international research focus.
Synthetic zirconium phosphate compounds mainly comprises laminate structure and the vesicular with molecular sieve structure at present.All in all the preparation method mainly comprises circumfluence method, direct precipitation method, hydro-thermal (or solvent thermal) synthesis method, template synthesis method etc.For example: the employing circumfluence method of delivering at material wall bulletin (MaterialsLeteers, 2004,58,3328～3331) in 2004 utilizes inorganic zirconates through two-step reaction, makes the sexangle zirconium phosphate of regular shape, Heat stability is good; 2003 also once at solid state ionics magazine (Solid StateIonics, 2003,162～163:185～190) deliver this kind of employing method and prepared good in thermal property and the good zirconium phosphate mesoporous material of degree of crystallinity, the people such as Zhang Rui that this method helps the formation Chinese University of Science and Technology of laminate structure adopt hydrothermal method successfully to prepare the stratified material of zirconium phosphate.2000 at materials chemistry (J.Mater.Chem., 2000, (10), also have on 2320-2324.) report water solution deposit when cetyl trimethylammonium bromide, cetylamine, sodium lauryl sulphate etc. are made template, to synthesize the porous calcium phosphate zirconium, but pore structure is bad.(Angew.Chem.Int.Ed.Engl 1996 to be published in German applied chemistry in 1996,35:2677-2678), make mineralizer with hydrofluoric acid, quadrol is that template has been synthesized the Zirconium phosphate crystal with three-dimensional spacious skeleton structure by hydrothermal synthesis method, be that template has been synthesized a series of hexafluorophosphoric acid zirconium crystalline materials with two dimension or three-dimensional structure with dissimilar organic amines again afterwards, this method synthetic material is removed poor heat stability in the process of template in roasting, and skeleton subsides easily.
The catalytic performance of zirconium phosphate not only is the acidity of itself, the prior matrix material that obtains behind other object (perhaps column-supporting agent) embedding people of being.On the one hand, make zirconium phosphate acidity have adjustable sex change, improved the geometrical property and the shape selectivity energy of pore passage structure; On the other hand, zirconium phosphate can be introduced all kinds of different active substances by various means, with catalyzer and the support of the catalyst for preparing different purposes, make it have the composite catalyzing performance, therefore will have very vast potential for future development to this class composite study.
Summary of the invention
The object of the present invention is to provide a kind of method with the hybridization of ionic liquid synthesizing nano-porous zirconium phosphate, it had both utilized the advantage of ionic liquid as solvent and structure directing agent, again the group of ionic liquid itself is introduced in the nano material, made prepared material have better character.
The object of the present invention is achieved like this:
A kind of method with the hybridization of ionic liquid synthesizing nano-porous zirconium phosphate comprises following concrete steps:
A), preparation ionic liquid
Equimolar 1-(2-amine ethyl) imidazoles hydrobromate and bromotrifluoromethane diethyl phosphoric acid are solvent with methyl alcohol, reflux at 80 ℃ and stir 48h, after reaction finishes, be cooled to room temperature, revolve to steam to remove and desolvate, obtain thick liquid, this liquid is water-soluble, add equimolar potassium hydroxide, normal temperature stirs 0.5h down, revolves to steam to remove to anhydrate, and the solid brominated sodium of elimination, vacuum-drying obtains ionic liquid 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromine; This ionic liquid amino-contained and phosphonate group functional group have following structure:
B), synthesizing nano-porous zirconium phosphate
With mass ratio is 1.5～4.5: 1.0～3.0: 2.0 above-mentioned ionic liquid, ZrOCl
2, water places the tetrafluoroethylene reactor, at 80～120 ℃ of reaction 12～36h; Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 8～10 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white, has following structure:
1-of the present invention (2-amine ethyl) imidazoles hydrobromate is that reference literature " synthesising communication was rolled up the 535th page (Synthesis Communication; 1991,21,535) in 1991 the 21st " is synthetic, the bromotrifluoromethane diethyl phosphoric acid is an analytical reagent, and methyl alcohol is analytical reagent.
The invention has the beneficial effects as follows:
(1), will have the ionic liquid grafting of basic functionality to go in the nano material, effectively improved the performance of solid nano material, greatly widen the range of application of functionalization material.
(2), have amidine functional group in the synthetic material, to CO
2Deng sour gas certain absorption property is arranged.
(3), the synthetic material has less pore passage structure, is a kind of good catalyzer.
(4), synthesis step is simple, easy to operate, reproducible results is good.
Description of drawings
Fig. 1 is the ion liquid infrared spectrogram of the present invention
Fig. 2 is the ion liquid hydrogen nuclear magnetic resonance spectrogram of the present invention
Fig. 3 is the infrared spectrogram of synthetic materials of the present invention
Fig. 4 is the XRD spectra of synthetic materials of the present invention
Fig. 5 is the transmission electron microscope photo of synthetic materials of the present invention
Embodiment
A), preparation ionic liquid
Equimolar 1-(2-amine ethyl) imidazoles hydrobromate and bromotrifluoromethane diethyl phosphoric acid are solvent with methyl alcohol, reflux at 80 ℃ and stir 48h; After reaction finishes, be cooled to room temperature, revolve to steam to remove and desolvate, obtain thick liquid, this liquid is water-soluble, add equimolar potassium hydroxide, normal temperature stirs 0.5h down, revolves to steam to remove to anhydrate, and the solid brominated sodium of elimination, vacuum-drying obtains ionic liquid 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromine.
B), nano-porous zirconium phosphate is synthetic
Get 1.5g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 2g ZrOCl
2, place the tetrafluoroethylene reactor in 100 ℃ of reaction 24h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 10 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
A), with embodiment 1
B), nano-porous zirconium phosphate is synthetic
Get 3g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 2g ZrOCl
2, place the tetrafluoroethylene reactor in 100 ℃ of reaction 24h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 9 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
A), with embodiment 1
B), nano-porous zirconium phosphate is synthetic
Get 4.5g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 2g ZrOCl
2, place the tetrafluoroethylene reactor in 100 ℃ of reaction 24h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 10 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
A), with embodiment 1
B), nano-porous zirconium phosphate is synthetic
Get 3g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 1g ZrOCl
2, place the tetrafluoroethylene reactor in 100 ℃ of reaction 24h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 8 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
Embodiment 5
A), with embodiment 1
B), nano-porous zirconium phosphate is synthetic
Get 3g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 3g ZrOCl
2, place the tetrafluoroethylene reactor in 100 ℃ of reaction 24h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 9 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
A), with embodiment 1
B), nano-porous zirconium phosphate is synthetic
Get 3g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 2g ZrOCl
2, place the tetrafluoroethylene reactor in 80 ℃ of reaction 24h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 10 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
A), with embodiment 1
B), nano-porous zirconium phosphate is synthetic
Get 3g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 2g ZrOCl
2, place the tetrafluoroethylene reactor in 120 ℃ of reaction 24h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 9 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
Embodiment 8
A), with embodiment 1
B), nano-porous zirconium phosphate is synthetic
Get 3g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 2g ZrOCl
2, place the tetrafluoroethylene reactor in 100 ℃ of reaction 12h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 8 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
Embodiment 9
A), with embodiment 1
B), nano-porous zirconium phosphate is synthetic
Get 3g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 2g ZrOCl
2, place the tetrafluoroethylene reactor in 100 ℃ of reaction 36h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 10 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
A), with embodiment 1
B), nano-porous zirconium phosphate is synthetic
Get 3g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 2g ZrOCl
2, place the tetrafluoroethylene reactor in 80 ℃ of reaction 36h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 9 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
Embodiment 11
A), with embodiment 1
B), nano-porous zirconium phosphate is synthetic
Get 1.5g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 2g ZrOCl
2, place the tetrafluoroethylene reactor in 80 ℃ of reaction 24h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 10 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
Embodiment 12
A), with embodiment 1
B), nano-porous zirconium phosphate is synthetic
Get 4.5g 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromide anion liquid, 2g water and 2g ZrOCl
2, place the tetrafluoroethylene reactor in 80 ℃ of reaction 24h.Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 10 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white powder.
Claims (1)
1. method with the hybridization of ionic liquid synthesizing nano-porous zirconium phosphate is characterized in that this method comprises following concrete steps:
A), preparation ionic liquid
Equimolar 1-(2-amine ethyl) imidazoles hydrobromate and bromotrifluoromethane diethyl phosphoric acid are solvent with methyl alcohol, reflux at 80 ℃ and stir 48h, after reaction finishes, be cooled to room temperature, revolve to steam to remove and desolvate, obtain thick liquid, this liquid is water-soluble, add equimolar potassium hydroxide, normal temperature stirs 0.5h down, revolves to steam to remove to anhydrate, and the solid brominated sodium of elimination, vacuum-drying obtains ionic liquid 1-(2-amine ethyl)-3-(2-diethoxy phosphine ester group) ethyl imidazol(e) bromine;
B), synthesizing nano-porous zirconium phosphate
With mass ratio is 1.5～4.5: 1.0～3.0: 2.0 above-mentioned ionic liquid, zirconium source, water place the tetrafluoroethylene reactor, at 80～120 ℃ of reaction 12～36h; Reaction is cooled to room temperature after finishing, and drips 28% ammoniacal liquor adjusting pH to 8～10 in product, gets solid product ethanol and water washing, and vacuum-drying, obtains the nano-porous zirconium phosphate of white; Wherein: the zirconium source is ZrOCl
2
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| CN104085869A (en) * | 2014-07-16 | 2014-10-08 | 辽宁石油化工大学 | Method for synthesizing spindly bismuth phosphate by adopting imidazole dihydric phosphate type ionic liquid |
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| CN104555971B (en) * | 2014-11-05 | 2017-07-04 | 盐城市锐金磨料磨具厂（普通合伙） | The method for preparing nanometer basic zirconium phosphate |
| CN104324585A (en) * | 2014-11-05 | 2015-02-04 | 朱忠良 | Method for purifying blast furnace flue gas by using ionic liquid |
| CN107814371A (en) * | 2017-10-25 | 2018-03-20 | 佛山杰致信息科技有限公司 | A kind of preparation method of basic zirconium phosphate mesoporous material |
| CN111003713A (en) * | 2019-12-20 | 2020-04-14 | 辽宁大学 | Method for preparing inorganic porous material based on ionic liquid ternary system |
| CN113070081B (en) * | 2021-04-01 | 2022-10-04 | 联科华技术有限公司 | Porous zirconium phosphate based monatomic catalyst for removing formaldehyde and preparation method thereof |
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| CN1383920A (en) * | 2002-05-16 | 2002-12-11 | 华东师范大学 | L-sulforamidate type chiral ionic liquid and its prepn |
| CN1385243A (en) * | 2002-06-07 | 2002-12-18 | 华东师范大学 | Diacetone acrylic amide type ionic liquid and preparation thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085869A (en) * | 2014-07-16 | 2014-10-08 | 辽宁石油化工大学 | Method for synthesizing spindly bismuth phosphate by adopting imidazole dihydric phosphate type ionic liquid |
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