CN109354695A - A method of coordination adjusts preparation sheet metal-organic framework materials - Google Patents
A method of coordination adjusts preparation sheet metal-organic framework materials Download PDFInfo
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- CN109354695A CN109354695A CN201811060372.8A CN201811060372A CN109354695A CN 109354695 A CN109354695 A CN 109354695A CN 201811060372 A CN201811060372 A CN 201811060372A CN 109354695 A CN109354695 A CN 109354695A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The present invention realizes the controlledly synthesis of sheet MOFs material by introducing urea as pattern regulator in synthetic system.Urea role during sheet MOFs Material growth is had studied in detail, the formation mechanism that coordination is adjusted is proposed.Urea is as alkali, as the temperature rises, the decomposition rate of urea is accelerated, system is in mild alkaline conditions, facilitate the deprotonation of ligand, it is remarkably improved the water solubility and deprotonation ability of ligand, the nucleation of crystal and going on smoothly for growth course is ensure that, the Cambium periodicity of MOF is made to change.On the other hand, hydrogen ion caused by the deprotonation of ligand can promote the decomposition of urea, so that the complexation reaction that metal ion and ligand are shown in is rapidly completed.The addition of urea not only significantly improves yield, while also obtaining the sheet MOFs material with good aqueous solubility and stability, lays the foundation for MOFs applied to sensory field.
Description
Technical field
The present invention relates to a kind of methods that coordination adjusts preparation sheet metal-organic framework materials, belong to materials synthesis neck
Domain.
Background technique
Metal organic framework (MOFs) material is a kind of novel hybrid inorganic-organic porous material, because of this kind of porous material
Diversity, the substantial amounts, specific surface area height, Kong Rong great, the easy functional modification of hole surface for expecting structure, store in gas, change
Credit is from catalysis, sensing and fuel cell etc. have shown good application prospect.The Nomenclature Composition and Structure of Complexes of MOFs material
Diversity and Modulatory character have great advantage being applied to every field.On the other hand, MOFs material is because of its excellent hair
Optical property, Subjective and Objective response characteristic abundant have received widespread attention applied to the research of luminescence sensor in recent years.But
Most luminous sensing and biology sensing is all to carry out in aqueous solution, the stability and dispersibility of MOFs material in the solution
It is bad to significantly limit its application.Therefore, it develops different structure and the MOFs material of good water solubility is very necessary.
Summary of the invention
It is an object of the invention to utilize urea as a kind of pattern regulator, have by one step hydro thermal method preparation water-soluble
The sheet MOFs material of property and stability.Have studied in detail urea work played in sheet MOFs Material growth process
With, propose coordination adjust formation mechanism.Urea is as alkali, and as the temperature rises, the decomposition rate of urea is accelerated, system
In mild alkaline conditions, facilitate the deprotonation of ligand, is remarkably improved the water solubility and deprotonation ability of ligand, deprotonation
Change NH2-H2After BDC ligand and metal ion are coordinated, nucleation and crystal growth are also quickly completed, and make the formation power of MOF
Change.On the other hand, hydrogen ion caused by the deprotonation of ligand can promote the decomposition of urea, so that metal ion
Complexation reaction between ligand is rapidly completed.Therefore, the addition of urea not only significantly improves yield, while also obtaining and have
The sheet MOFs material of good aqueous solubility and stability has apparent advantage for sensory field.
Technical scheme is as follows:
(1) ligand 2- amino terephthalic acid (TPA) (NH is added into metal salt solution under magnetic stirring2-H2BDC), stir
After a period of time, urea is added, forms forerunner's liquid suspension.
(2) mixture is placed in polytetrafluoroethylene (PTFE) autoclave, hydro-thermal reaction is for a period of time.
(3) hydrothermal product is taken out, goes out product with excessive acetone precipitation, product is collected by centrifugation.
(4) it purifies: product is dispersed in DMF the purifying that flows back, decompression is filtered, washed with ethyl alcohol, is dried in vacuo, and is received
Collect product.
Invention effect
Compared with prior art, the present invention has the advantage that
(1) the sheet MOFs of the hydrothermal synthesis method preparation novel in shape adjusted using coordination；
(2) amido modified sheet MOFs material has good water-soluble and water stability.
Specific embodiment
Embodiment 1
3mmol Cu(NO3)2·3H2After O 35mL deionized water dissolving, 3mmol NH is added under magnetic stirring2-
H2BDC stirs 30min, and 6mmol urea is added in said mixture, continues to stir 30min.Then the mixture that will be obtained
It is placed in 50mL polytetrafluoroethylene (PTFE) autoclave, after reacting 10h respectively at 150 DEG C, is cooled to room temperature.By excessive third
Ketone is added in solution, generates a large amount of precipitatings, collects to obtain bottle-green sediment with 10000rpm/min centrifugation 15min.It is heavy
Starch is dispersed in 120 DEG C of reflux 6h in the DMF solution of 100mL, then gained sediment is depressurized and is filtered, and obtains bottle green product.So
Multiple with a large amount of DMF or acetone washing afterwards, product is redispersed in 100mL dehydrated alcohol, continues stirring for 24 hours, finally by product
Decompression suction filtration is carried out again, obtains solid product under the conditions of 70 DEG C, and vacuum drying removes ethyl alcohol, obtains product, calculates yield.
Embodiment 2
3mmol Fe(NO3)2·6H2After O 35mL deionized water dissolving, 3mmol NH is added under magnetic stirring2-
H2BDC stirs 30min, and 6mmol urea is added in said mixture, continues to stir 30min.Then the mixture that will be obtained
It is placed in 50mL polytetrafluoroethylene (PTFE) autoclave, after reacting 5h respectively at 150 DEG C, is cooled to room temperature.By excessive third
Ketone is added in solution, generates a large amount of precipitatings, collects to obtain bottle-green sediment with 10000rpm/min centrifugation 15min.It is heavy
Starch is dispersed in 120 DEG C of reflux 6h in the DMF solution of 100mL, then gained sediment is depressurized and is filtered, and obtains bottle green product.So
Multiple with a large amount of DMF or acetone washing afterwards, product is redispersed in 100mL dehydrated alcohol, continues stirring for 24 hours, finally by product
Decompression suction filtration is carried out again, obtains solid product under the conditions of 70 DEG C, and vacuum drying removes ethyl alcohol, obtains product, calculates yield.
Embodiment 3
3mmol AlCl3·6H2After O 35mL deionized water dissolving, 3mmol NH is added under magnetic stirring2-H2BDC,
30min is stirred, 6mmol urea is added in said mixture, continues to stir 30min.Then obtained mixture is placed in
In 50mL polytetrafluoroethylene (PTFE) autoclave, after reacting 5h respectively at 150 DEG C, it is cooled to room temperature.Excessive acetone is added
Enter into solution, generate a large amount of precipitatings, collects to obtain bottle-green sediment with 10000rpm/min centrifugation 15min.Sediment
120 DEG C of reflux 6h in the DMF solution of 100mL are dispersed in, then gained sediment is depressurized and is filtered, obtain bottle green product.Then it uses
A large amount of DMF or acetone washing are multiple, and product is redispersed in 100mL dehydrated alcohol, continue stirring for 24 hours, again by product finally
Decompression suction filtration is carried out, obtains solid product under the conditions of 70 DEG C, vacuum drying removes ethyl alcohol, obtains product, calculates yield.
Claims (3)
1. a kind of method that coordination adjusts preparation sheet metal organic framework (MOFs) material, it is characterised in that including following five
A step:
(1) ligand 2- amino terephthalic acid (TPA) (NH is added into metal salt solution under magnetic stirring2-H2BDC), one section is stirred
After time, urea is added, forms forerunner's liquid suspension；
(2) mixture is placed in polytetrafluoroethylene (PTFE) autoclave, hydro-thermal reaction is for a period of time；
(3) hydrothermal product is taken out, goes out product with excessive acetone precipitation, product is collected by centrifugation；
(4) it purifies: product is dispersed in DMF the purifying that flows back, decompression is filtered, washed with ethyl alcohol, is dried in vacuo, and production is collected
Object；
(5) water stability and water solubility of product are investigated.
2. method according to claim 1, it is characterised in that urea forms sheet material as pattern regulator.
3. method according to claim 1, feature can be used various metal salts as reactant, can prepare each eka-gold
Belong to organic framework material, such as Cu-MOF, Al-MOF, Fe-MOF.
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| CN201811060372.8A CN109354695A (en) | 2018-09-12 | 2018-09-12 | A method of coordination adjusts preparation sheet metal-organic framework materials |
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| CN201811060372.8A CN109354695A (en) | 2018-09-12 | 2018-09-12 | A method of coordination adjusts preparation sheet metal-organic framework materials |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776812A (en) * | 2019-02-21 | 2019-05-21 | 河北工业大学 | The preparation method of Cu base two-dimensional sheet MOFs material |
| CN112250876A (en) * | 2020-09-24 | 2021-01-22 | 温州大学 | Preparation method of two-dimensional IRPY type MOF material and functionalized M @ IRPA-MOF supported catalyst |
| CN114426677A (en) * | 2022-01-04 | 2022-05-03 | 安徽农业大学 | Amino modified metal organic framework material, preparation method and application thereof |
Citations (2)
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| US20100125957A1 (en) * | 2008-11-25 | 2010-05-27 | Xiaoyong Hong | Solid Polymeric Colorant Compositions |
| CN104330400A (en) * | 2014-10-24 | 2015-02-04 | 南京晓庄学院 | CdS nanoparticle-based nano developing probe as well as preparation method and application thereof |
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2018
- 2018-09-12 CN CN201811060372.8A patent/CN109354695A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100125957A1 (en) * | 2008-11-25 | 2010-05-27 | Xiaoyong Hong | Solid Polymeric Colorant Compositions |
| CN104330400A (en) * | 2014-10-24 | 2015-02-04 | 南京晓庄学院 | CdS nanoparticle-based nano developing probe as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| TING LU ET AL: ""Amino-Functionalized Metal-Organic Frameworks Nanoplates-Based Energy Transfer Probe for Highly Selective Fluorescence Detection of Free Chlorine"", 《ANALYTICAL CHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776812A (en) * | 2019-02-21 | 2019-05-21 | 河北工业大学 | The preparation method of Cu base two-dimensional sheet MOFs material |
| CN109776812B (en) * | 2019-02-21 | 2021-11-23 | 河北工业大学 | Preparation method of Cu-based two-dimensional flaky MOFs material |
| CN112250876A (en) * | 2020-09-24 | 2021-01-22 | 温州大学 | Preparation method of two-dimensional IRPY type MOF material and functionalized M @ IRPA-MOF supported catalyst |
| CN114426677A (en) * | 2022-01-04 | 2022-05-03 | 安徽农业大学 | Amino modified metal organic framework material, preparation method and application thereof |
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