CN108329486A - A kind of preparation method and application of the metal-organic framework materials of hybrid mesoporous structure - Google Patents
A kind of preparation method and application of the metal-organic framework materials of hybrid mesoporous structure Download PDFInfo
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Abstract
The present invention provides a kind of preparation method and application of the metal-organic framework materials of hybrid mesoporous structure.Method provided by the invention is that either intermediate product is obtained by the reaction with corresponding organic ligand or metal ion in the gel micro-ball of organic ligand by metal ion, gel template is removed by elution, the micropore canals being not only self-assembly of containing metal ion and organic ligand are obtained, but also with the hybrid structure metal-organic framework materials for removing the mesopore orbit that gel skeleton leaves.Hybrid mesoporous structural metal organic framework material preparation method applicability provided by the invention is wide, and the duct pore diameter range of product is wide and adjustable, and stable structure is widely used, has broad application prospects in enzyme immobilization carrier, organic dyestuff removing etc..
Description
Technical field
The invention belongs to technical field of nanometer material preparation, it particularly relates to which a kind of metal of hybrid mesoporous structure has
The preparation method and application of machine framework material.
Background technology
Metal-organic framework materials are a kind of more porous nanometer materials of Recent study.Metal-organic framework materials are real
It is a kind of crystal that the coordination by between metal and organic ligand is formed in matter, since its pore passage structure and physico-chemical property can
With in molecular level up regulation, so detaching and storing in gas in recent years, heterogeneous catalysis, the area researches such as medicament slow release are very
It is more.
The duct of metal-organic framework materials is being self-assembly of by metal and organic ligand, is limited to organic match
The size of body, most metals organic framework material are all micropore canals structure, and which limits its applications.It is organic to adjust metal
The classical way of framework material pore passage structure is to achieve the purpose that adjust pore passage structure using various sizes of organic ligand.Than
Such as, it is reachable using the 2,5-Dihydroxyterephthalic acid of single phenyl ring as starting material to have synthesized longest for Omar M.Yaghi seminars
The backbone ligand of 11 phenyl ring, and form metal-organic framework materials, the gold of gained using these ligands and metal ion
(Science, 2012,336,1018-1023) can be adjusted within the scope of 1.4-9.8nm by belonging to organic framework material aperture.But
This method applicability is limited, and the synthesis of ligand is time-consuming and laborious, while with the increase of organic ligand size, and metal is organic
The stability of framework material pore passage structure can be affected.Inspired by molecular sieve preparation process, Qiu et al. report for the first time with
Common template cetyltrimethylammonium bromide is template during system with molecular sieve for preparing is standby, has been synthesized with meso-hole structure
HKUST-1(Angew.Chem.2008,120,9629-9633).After this, by the method for template that microcellular structure is golden
Category organic framework material is adjusted to the report of meso-hole structure with regard to more, and the type of template is also developed to from surfactant
Block polymer.But reported these are more demanding to experimental implementation by the method for template adjustment aperture because
The micellar structure of surfactant or block polymer and metal ion or organic ligand formation is very unstable, which limits
The application prospect of this method, it is therefore desirable to new method be provided and achieve the purpose that adjust metal-organic framework materials aperture.
Invention content
In order to solve the above technical problems, the present invention provides a kind of metal-organic framework materials of hybrid mesoporous structure and its
Preparation method and purposes.
The metal-organic framework materials of hybrid mesoporous structure of the present invention had both contained metal ion and organic ligand certainly
Assemble the micropore canals formed, and the mesopore orbit left with removal gel skeleton.
The preparation method of the metal-organic framework materials of above-mentioned hybrid mesoporous structure：By metal by way of physically encapsulation
Ion or organic ligand are enriched in gel micro-ball, then intermediate product is obtained by the reaction with corresponding organic ligand or metal ion,
Gel template is removed by elution, obtains the metal-organic framework materials of hybrid mesoporous structure.
Further, in the preparation method of the metal-organic framework materials of above-mentioned hybrid mesoporous structure, the gel micro-ball
Preparation method be:It is added soluble metallic salt into liquid gel solution, the mass ratio of metal salt and gel is more than 1:1 and small
In 20:1；The above-mentioned liquid gel solution containing metal salt is transferred in strong-hydrophobicity organic phase, organic phase and gel solution
Volume ratio be more than 5:1 and be less than 20:1, contain water-in-oil emulsifier, the volume of organic phase and emulsifier in above-mentioned organic phase
Than being more than 20:1 and be less than 50:1, after emulsification, the phase transition process that gel is completed by quenching obtains being enriched with metal ion
The microballoon of gel state.
Further, the gel is melamine-bigcatkin willow acid hydrogel or melamine-core yellow hydrogel.
Further, the organic phase is n-hexane, petroleum ether or atoleine.
Further, melamine-salicylic acid gel template prepares the metal-organic framework materials of hybrid mesoporous structure
Process is as follows：
Melamine, salicylic acid are weighed, simultaneously deionized water is added in metal salt, melamine and salicylic acid in final mixture
Molar ratio be more than 0.5:1 and be less than 3:1, a concentration of 0.5-2mg/mL of the two in water；The matter of metal salt and melamine
Amount is than being more than 1:1 and be less than 20:1；Above-mentioned mixed liquor is heated to 50-90 degrees Celsius, is transferred them to after being kept for 10-15 minutes
In mutually synthermal organic phase, contain water-in-oil emulsifier in the organic phase, by mechanical agitation emulsification 20-60 minutes,
Then it places it in plastic in ice-water bath and is kept stirring；Then excessive organic ligand solution is added, it is small to stir 12-24 at room temperature
When, finally by centrifuging product, and using ethyl alcohol washing purifying, the metal that hydridization pore passage structure is obtained after dry is organic
Framework material.
Further, melamine-riboflavin gel template prepares the metal-organic framework materials of hybrid mesoporous structure
Process is as follows：
Melamine, riboflavin are weighed, simultaneously deionized water is added in metal salt, melamine and salicylic acid in final mixture
Molar ratio be more than 0.5:1 and be less than 3:1, a concentration of 0.1-3mg/mL of the two in water；The matter of metal salt and melamine
Amount is than being more than 1:1 and be less than 50:1；Above-mentioned mixed liquor is heated to 90-130 degrees Celsius, is shifted after being kept for 10-15 minutes
Into mutually synthermal organic phase, contain water-in-oil emulsifier in the organic phase, passes through mechanical agitation emulsification 20-60 points
Then clock places it in plastic in ice-water bath and is kept stirring；Then excessive organic ligand solution is added, stirs 12- at room temperature
24 hours, be to obtain the metal of hydridization pore passage structure after dry finally by centrifugation product, and using ethyl alcohol washing purifying
Organic framework material.
Using the metal-organic framework materials of above-mentioned hybrid mesoporous structure as enzyme immobilization carrier or organic dyestuff scavenger
Application.
The present invention obtains following technique effect：
1) metal-organic framework materials for the hybrid mesoporous structure that the present invention obtains both contain metal ion and organic ligand
The micropore canals being self-assembled into, and the mesopore orbit left with removing gel skeleton, having widened tradition only has micropore canals
Metal-organic framework materials application range.
2) the duct pore diameter range of the metal-organic framework materials for the hybrid mesoporous structure that the present invention obtains is wide and adjustable,
Stable structure, preparation method applicability is wide, by selecting variety classes gel skeleton that can match different metal organic backbone
The synthesis condition of material.Preparation method provided by the invention overcomes traditional modified ligand with the method applicability of hole diameter enlargement
It is limited and be easy to cause the unstable disadvantage of pore passage structure, and deposited using the method for surfactant-based template adjustment aperture
In the drawback that experiment condition is difficult to control.
3) metal-organic framework materials of hybrid mesoporous structure that the present invention obtains are widely used, enzyme immobilization carrier,
Organic dyestuff removing etc. has potential application value.
Description of the drawings
Fig. 1 is hybrid mesoporous metal organic framework ZIF-8 (HZIF-8) and the standard microwell metal organic framework of synthesis
The scanning electron microscope diagram of ZIF-8 (SZIF-8)；
Fig. 2 is the HZIF-8 of synthesis, the X-ray diffractogram of SZIF-8；
Fig. 3 is the HZIF-8 of synthesis, the isothermal nitrogen adsorption desorption curve graph of SZIF-8；
Fig. 4 is the HZIF-8 of synthesis, the graph of pore diameter distribution of SZIF-8；
Fig. 5 is HZIF-8 immobilised enzymes, SZIF-8 immobilised enzymes, free enzyme catalytic performance figure in different concentration of substrate；
Fig. 6 is HZIF-8-1, and SZIF-8 adsorbs organic dyestuff eosin Y disodium salt effect contrast figure.
Specific implementation mode
With reference to specific embodiment to a kind of metal-organic framework materials of hybrid mesoporous structure of the present invention
And its preparation method and application be described further, but protection scope of the present invention is not limited to this.
The synthesis of 1 hybrid mesoporous structure HZIF-8-1 of embodiment
By 0.0477g melamines, 0.0523g salicylic acids, 0.2975g zinc nitrates (six crystallizations water) are blended in 10mL
In ionized water, and mixed liquor is heated to 75 degrees Celsius, mixed liquor becomes colorless transparency liquid at this time.Mixed liquor is at 75 degrees Celsius
It is poured into the synthermal atoleine of the 200mL phases containing 10mL emulsifiers Span85 after keeping 15min.It is stirred by machinery
Mix emulsification, emulsification times 30min, rotating speed 400rpm.Then, emulsion is transferred in ice-water bath, is kept under stirring condition
1h promotes the progress of gelation.It is subsequently added into the aqueous solution 10mL of 0.8211g 2-methylimidazoles, continues to stir 12h.Finally,
By centrifuging product, and using ethyl alcohol washing purifying, product is obtained after dry.
The synthesis of 2 hybrid mesoporous structure HZIF-8-2 of embodiment
By 3mg melamines, 27mg riboflavin is mixed with 100mL deionized waters, and 120 degrees Celsius are heated under counterflow condition
And 15min is kept, solution is yellow transparent shape at this time.Above-mentioned solution 10mL is taken, and 0.2975g zinc nitrates (six are added thereto
A crystallization water), it is poured into the synthermal liquid of the 200mL phases containing 10mL emulsifiers Span85 after keeping 120 degrees Celsius of 5min
In body paraffin.Pass through mechanical agitation emulsification, emulsification times 30min, rotating speed 400rpm.Then, emulsion is transferred to ice water
In bath, 1h is kept under stirring condition, promotes the progress of gelation.Then, 0.8211g 2- methyl is added into above-mentioned emulsion
The aqueous solution 10mL of imidazoles continues to stir 12h.Finally, by centrifuging product, and using ethyl alcohol washing purifying, after dry
Obtain product.
The characterization of pore-size distribution in 3 metal-organic framework materials of embodiment
Experimental method：By taking HZIF-8-1 as an example, deaerates at 100 degrees Celsius after 6h, nitrogen adsorption desorption curve has been carried out to it
Characterization.
By Fig. 3, it is apparent that HZIF-8-1 in low-pressure area other than having adsorption capacity for nitrogen, adsorbed in middle pressure
There is apparent adsorption capacity for nitrogen in area, illustrates that zinc nodes of the HZIF-8-1 with SZIF-8 itself is complexed to be formed with 2-methylimidazole
Micropore canals, also remove the mesopore orbit that generates after gel template.The pore volume of HZIF-8-1 is 0.80mL/g, than
SZIF-8 improves 19.4%, and mesoporous pore volume accounting 73.8%.In terms of specific surface area, HZIF-8-1 476m2/ g is
The 34.1% of ZIF-8, this is because the duct of microcellular structure compares the big contribution bigger of surface area, and micropore only accounts in HZIF-8
26.2%.HZIF-8-1 mesopore orbits average pore size is 2.56nm it can be seen from the graph of pore diameter distribution of Fig. 4, and has aperture
The presence in the duct more than 10nm, these ducts makes the application potential bigger of HZIF-8.
Applications of 4 HZIF-8-1 of embodiment in multienzyme immobilization
By infusion process, two kinds of large biological molecule horseradish peroxidases and grape oxidase enzyme are fixed on jointly
The inside of HZIF-8, and it is catalyzed a cascade reaction with it.The substrate of the reaction is glucose and ABTS (2'- hydrazines-bis--
3- ethyl benzo thiazole phenanthroline -6- sulfonic acid), glucose converts glucose into glucose under the action of glucose oxidase first
Acid and hydrogen peroxide, then hydrogen peroxide ABTS is oxidized to oxidation state ABTS under the catalytic action of horseradish peroxidase+。
Compared with SZIF-8 immobilised enzymes, the catalysis highest response rate of HZIF-8-1 immobilised enzymes improves 6.9 times；With free enzyme phase
Has the maximum reaction rate of free enzyme 89.6% than, HZIF-8, and maximum reaction rate remains to reach after reusing 25 times
To the 56.4% of original value.In addition, HZIF-8-1 immobilised enzymes is more preferable than free enzyme to the compatibility of substrate, Michaelis constant is
2.6mmol/L, the 27.4% of only free enzyme.
Applications of 5 HZIF-8-1 of embodiment in adsorbing organic dyestuff
Using eosin Y disodium salt as research object, HZIF-8-1 and ZIF-8 have been investigated to its adsorption capacity not
Together.Under identical experiment condition, compared with ZIF-8, HZIF-8-1 significantly increases the adsorption capacity of eosin Y disodium salt,
Dye strength is lower in solution after absorption.
Claims (8)
1. a kind of metal-organic framework materials of hybrid mesoporous structure, which is characterized in that both contain metal ion and organic ligand
The micropore canals being self-assembly of, and the mesopore orbit left with removal gel skeleton.
2. a kind of preparation method of the metal-organic framework materials of hybrid mesoporous structure, which is characterized in that pass through physically encapsulation
Metal ion or organic ligand are enriched in gel micro-ball by mode, then are obtained by the reaction with corresponding organic ligand or metal ion
Intermediate product removes gel template by elution, obtains the metal organic framework of hybrid mesoporous structure as described in claim 1
Material.
3. the preparation method of the metal-organic framework materials of hybrid mesoporous structure according to claim 2, which is characterized in that
The preparation method of the gel micro-ball is:Soluble metallic salt, the quality of metal salt and gel are added into liquid gel solution
Than being more than 1:1 and be less than 20:1；The above-mentioned liquid gel solution containing metal salt is transferred in strong-hydrophobicity organic phase, it is organic
Mutually it is more than 5 with the volume ratio of gel solution:1 and be less than 20:1, contain water-in-oil emulsifier in above-mentioned organic phase, organic phase with
The volume ratio of emulsifier is more than 20:1 and be less than 50:1, after emulsification, the phase transition process that gel is completed by quenching is enriched with
There is the microballoon of the gel state of metal ion.
4. the preparation method of the metal-organic framework materials of hybrid mesoporous structure according to claim 3, which is characterized in that
The gel is melamine-bigcatkin willow acid hydrogel or melamine-core yellow hydrogel.
5. the preparation method of the metal-organic framework materials of hybrid mesoporous structure according to claim 4, which is characterized in that
The organic phase is n-hexane, petroleum ether or atoleine.
6. the preparation method of the metal-organic framework materials of hybrid mesoporous structure according to claim 4, which is characterized in that
The process for the metal-organic framework materials that melamine-salicylic acid gel template prepares hybrid mesoporous structure is as follows：
Melamine, salicylic acid are weighed, simultaneously deionized water is added in metal salt, and melamine rubs with salicylic in final mixture
You are than being more than 0.5:1 and be less than 3:1, a concentration of 0.5-2mg/mL of the two in water；The mass ratio of metal salt and melamine
More than 1:1 and be less than 20:1；Above-mentioned mixed liquor is heated to 50-90 degrees Celsius, is transferred them to after being kept for 10-15 minutes identical
In the organic phase of temperature, contain water-in-oil emulsifier in the organic phase, by mechanical agitation emulsification 20-60 minutes, then
It places it in plastic in ice-water bath and is kept stirring；Then excessive organic ligand solution is added, stirs 12-24 hours at room temperature,
It is to obtain the organic bone of metal of hydridization pore passage structure after dry finally by centrifugation product, and using ethyl alcohol washing purifying
Frame material.
7. the preparation method of the metal-organic framework materials of hybrid mesoporous structure according to claim 4, which is characterized in that
The process for the metal-organic framework materials that melamine-riboflavin gel template prepares hybrid mesoporous structure is as follows：
Melamine, riboflavin are weighed, simultaneously deionized water is added in metal salt, and melamine rubs with salicylic in final mixture
You are than being more than 0.5:1 and be less than 3:1, a concentration of 0.1-3mg/mL of the two in water；The mass ratio of metal salt and melamine
More than 1:1 and be less than 50:1；Above-mentioned mixed liquor is heated to 90-130 degrees Celsius, phase is transferred them to after being kept for 10-15 minutes
In synthermal organic phase, contain water-in-oil emulsifier in the organic phase, by mechanical agitation emulsification 20-60 minutes, so
After place it in plastic in ice-water bath and be kept stirring；Then excessive organic ligand solution is added, it is small to stir 12-24 at room temperature
When, finally by centrifuging product, and using ethyl alcohol washing purifying, the metal that hydridization pore passage structure is obtained after dry is organic
Framework material.
8. the metal-organic framework materials for the hybrid mesoporous structure that any one in claim 2 to 7 obtains are fixed as enzyme
Change the application of carrier or organic dyestuff scavenger.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109046279A (en) * | 2018-08-02 | 2018-12-21 | 南京理工大学 | Melamine@ZIF-67 modified sponge oil absorption material and preparation method thereof |
| CN110170337A (en) * | 2019-05-20 | 2019-08-27 | 辽宁石油化工大学 | Metal-organic framework materials MIL-53(Fe) hole-closing structure preparation method |
| CN111450257A (en) * | 2020-03-18 | 2020-07-28 | 温州医科大学 | Composite nano material based on ZIF-8 and riboflavin, and preparation method and application thereof |
| CN111569849A (en) * | 2020-05-18 | 2020-08-25 | 北京石油化工学院 | Immobilized metal chelate chromatography medium and preparation method and application thereof |
| CN114349182A (en) * | 2022-01-07 | 2022-04-15 | 南京工业大学 | Method for degrading bisphenol A in solutions with different pH values by using metal organic framework ZIF-8 immobilized laccase |
| CN115957177A (en) * | 2022-08-31 | 2023-04-14 | 东华大学 | Nanoparticle with cascade enzyme catalytic activity and diabetes immunoregulation and preparation and application of multifunctional hydrogel thereof |
| CN116120580A (en) * | 2023-01-31 | 2023-05-16 | 上海交通大学 | Ordered bicontinuous structure metal organic framework material SP-ZIF-8, preparation method and application thereof |
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