CN108114699A - The preparation method and thus obtained nano material of a kind of adjustable multi-stage porous metal organic framework nano material in aperture and its application - Google Patents
The preparation method and thus obtained nano material of a kind of adjustable multi-stage porous metal organic framework nano material in aperture and its application Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the adjustable multi-stage porous metal organic framework nano material in aperture, including：The synthetic microporous zirconium-based metallic organic backbone of method that terephthalic acid (TPA) is passed through into solvent heat under the conditions of existing for conditioning agent with zirconates；By micropore zirconium-based metallic organic backbone dry, micropore zirconium-based metallic organic backbone activated after low boiling point solvent activation；The micropore zirconium-based metallic organic backbone of activation is dispersed at 25 180 DEG C in the monocarboxylic acid of 0.8 5.6mol/L and is etched, obtains multi-stage porous metal organic framework nano material.The invention further relates to the obtained adjustable multi-stage porous metal organic framework nano material in aperture and its applications.In short, preparation in accordance with the present invention, during monocarboxylic acid etches and to form multi-stage porous, partial pore is retained, this multi-stage porous metal organic framework caused has the chemical stability similar with former porous skeleton and thermal stability.
Description
Technical field
The present invention relates to porous materials and field of enzyme immobilization, and in particular to a kind of adjustable multistage mesoporous metal in aperture is organic
The preparation method of skeleton nano material and thus obtained nano material and its application.
Background technology
Metal organic framework (Metal-organic frameworks, MOFs) by metal cluster and organic is matched somebody with somebody as a kind of
The porous material that body self assembly forms was obtaining extensive research and development at full speed in recent years.With conventional porous materials phase
Than MOFs has the diversity of programmable topological structure, adjustable physicochemical characteristics and species.In gas
Adsorb with separating, being catalyzed, the fields such as molecule sensing and drug release achieve and be widely applied (Chem.Soc.Rev.,
2017,46,126-157；Chem.Rev.,2015,115,11079-11108；Dalton Trans.,2016,45,18003-
18017；CrystEngComm,2015,17,706-718).However, it will be apparent that the size and duct environment in hole determine guest molecule
Spread condition of the son in metal organic framework, and guest molecule can be good in MOFs before diffusion is above application
It carries.However, the most MOFs that can be synthesized at present are pure microcellular structures, which greatly limits MOFs to relate to
And the application in macromolecular field.Therefore, development one kind can be prepared with multi-stage porous (not only comprising micropore but also comprising mesoporous)
MOFs is particularly significant and significant.
Recent years, some prepare the method for multi-stage porous metal organic framework by proposition successively.Such as California Berkeley
The Yaghi professors (Science, 2012,336,1018-1023) of university are the mesoporous of class by extending ligand sizes to be prepared for one
Metal organic framework, MOF-74 are micropore MOFs, the Yaghi professors formed by 2,5-Dihydroxyterephthalic acid and divalent metal
The number of phenyl ring is increased to most 11 by one, so as to increase the hole cage size of MOFs, maximum can reach 10nm；De Ke
The Zhou Hongcai professors (J.Am.Chem.Soc., 2012,134,126-129) of Sa Si A＆M universities are by using CTAB as template
Agent has synthesized Cu-BTC multi-stage porous metal organic frameworks, and the micella formed by CTAB is template, citric acid as template and
The bridging agent of metallic site makes template occupy certain space in MOFs, so as to form the vermiform of 15 rans
Duct；In addition other people develop etching method (Chem.Sci., 2017,8,6799-6803), ligand break method
(Nat.Commun., 2017,8,15356) and construction defect (Angew.Chem.Int.Ed., 2017,129,578-582) etc.
Method.But these methods have the defects of bigger and limitation.For example extending ligand method, the extension of one side ligand can make
Into the interspersed of duct, cause the reduction of porosity and specific surface area, the extension of another aspect ligand can cause the unstable of structure
Property, this is very unfavorable to the application of material；And some multi-stage porous metal organic frameworks can be prepared really by template,
But many times the removal of template can bring caving in for duct, and the presence of template can cause office when MOFs is crystallized
Portion is decrystallized；And other most of preparation methods are also only applicable to the MOFs of some stability difference, the multi-stage porous prepared
MOFs also because of chemical stability and poor thermal stability the reason for application in many fields be restricted.It is ground from both domestic and external above
Study carefully present situation and can be seen that researcher in terms of the preparation method of development multi-stage porous with very high enthusiasm, but worked out
Method has significant limitations, and the MOFs stability differences of the multi-stage porous of preparation are a urgent issues, therefore, development one
Kind simple effective method goes the grading-hole MOFs for preparing stabilization to be one application value and challenging work very much
Make.
The content of the invention
The present invention is intended to provide a kind of preparation method of adjustable multi-stage porous metal organic framework nano material in aperture and
Thus obtained nano material and its application, so as to using the nano material meso-hole structure large biological molecule is adsorbed or
Person immobilizes enzyme molecule, and it is small both to have maintained the good stability of skeleton using the microcellular structure of the nano material
Journal of Molecular Catalysis substrate provides transmission channel.
The preparation method of the adjustable multi-stage porous metal organic framework nano material in aperture provided by the invention, including walking as follows
Suddenly：S1, the synthetic microporous zirconium-based metallic of method that terephthalic acid (TPA) is passed through into solvent heat under the conditions of existing for conditioning agent with zirconates
Organic backbone, wherein, zirconates provides zirconium oxygen cluster as node, and terephthalic acid (TPA) is coordinated as connector and zirconium oxygen cluster from group
Dress forms three-dimensional porous crystalline framework；S2 by the drying after low boiling point solvent activation of micropore zirconium-based metallic organic backbone, is obtained
The micropore zirconium-based metallic organic backbone of activation；The micropore zirconium-based metallic organic backbone of activation is dispersed in by S3 at 25-180 DEG C
It is etched in the monocarboxylic acid of 0.8-5.6mol/L, obtains multi-stage porous metal organic framework nano material, wherein, monocarboxylic acid substitution
Organic ligand and with zirconium oxygen cluster be coordinated.
In the present invention, conditioning agent controls particle size by the effect with terephthalic acid (TPA) organic ligand competitive coordination
Size, when an organic ligand is substituted by two monocarboxylic acids, this organic ligand will depart from from skeleton；When
When the organic ligand that one zirconium oxygen cluster is coordinated is substituted by monocarboxylic acid, this zirconium oxygen cluster can also be fallen from skeleton
Fall, in skeleton the disengaging of substantial amounts of organic ligand and zirconium oxygen cluster multi-stage porous is born.Therefore, it is monocarboxylic by controlling
The temperature of acidity and concentration, the time of etching or etching can control the quantity of organic ligand and the disengaging of zirconium oxygen cluster, so as to
Achieve the purpose that control multi-stage porous hole parameter.For example, being adjusted by concentration, can aperture be become in the range of 3-100nm
Change；It is adjusted by temperature, can aperture be changed in the range of 3-50nm；By time adjustment, can aperture be existed
Change in the range of 3-25nm.
The zirconates is zirconium chloride, six water oxygen zirconium chlorides or zirconium nitrate.
The conditioning agent is benzoic acid.
The molar ratio of terephthalic acid (TPA), zirconates and conditioning agent is 1：1：20.
Step S1 is specially：Zirconium chloride, terephthalic acid (TPA) dissolving are formed into the first solution in a solvent, by conditioning agent
It adds in the first solution and forms the second solution, inorganic acid is added in, the 3rd solution is formed in the second solution, ultrasound is quiet after 120 DEG C
It puts to obtain micropore zirconium-based metallic organic backbone.
The solvent is N, and N dimethyl amide, which is concentrated hydrochloric acid.
Step S2 is specially：Acetone soak micropore zirconium-based metallic organic backbone.
The monocarboxylic acid is formic acid, acetic acid, propionic acid or butyric acid.Obviously, the acidity of formic acid>The acidity of acetic acid>The acid of butyric acid
Property>The acidity of propionic acid, acid higher etching power are stronger.Gradually deepen moreover, etch period etches degree in the range of 0-6h,
Degree is etched after 6h substantially no longer to change.As temperature raises in 25-180 DEG C of temperature range, etching degree is deepened.For example,
For propionic acid, also increase as concentration increases etching degree in the range of concentration 0.8-5.6mol/L, concentration is less than 0.8mol/
L, propionic acid are not enough to replace ligand, and concentration is too high can replace excessive ligand structure is caused thoroughly to be destroyed.
The aperture adjustable multi-stage porous metal organic framework nanometer provided by the invention obtained according to above-mentioned preparation method
Material, wherein, which has meso-hole structure and microcellular structure.
The present invention also provides a kind of according to above-mentioned multi-stage porous metal organic framework applications to nanostructures, wherein, this is more
Grade mesoporous metal organic backbone nano material is used to adsorb large biological molecule cytochrome c and immobilized HRP.
The application includes the following steps：Multi-stage porous zirconium-based metallic organic backbone nano particle is scattered in HEPES bufferings by B1
In liquid in (pH=7.4) solution；B2 adds in large biological molecule in aqueous solution, and stirring is so that large biological molecule fully diffuses to
In the duct of nano particle.Front and rear supernatant will be adsorbed and carry out ultraviolet-visible spectrum absorption test, arrived according to absworption peak 400
The adsorbance (corresponding diagram 10A) for changing to determine enzyme of absorption peak strength between 410.
The multi-stage porous zirconium-based metallic organic backbone nano particle can adsorb the cytochrome c and 94mg/g of 214mg/g
Horseradish peroxidase.
The application further includes following steps：Horseradish peroxidase is loaded in the multi-stage porous zirconium base etched at 180 DEG C by C1
In metal organic framework, and in HEPES buffer solutions o-phenylenediamine is catalyzed to test the enzymatic after its immobilization
Performance, the simple multi-stage porous zirconium-based metallic organic backbone of the results show does not possess catalytic performance, and loads horseradish peroxidase
There is good catalytic performance (corresponding diagram 10B) afterwards；C2, the multi-stage porous zirconium-based metallic for being loaded with horseradish peroxidase is organic
Skeleton is catalyzed o-phenylenediamine in the HEPES buffer solutions there are different organic solvents, tests the enzyme activity of immobilised enzymes
Property, to determine the anti-organic solvent properties of immobilised enzymes, the results show is supported on peppery on multi-stage porous zirconium-based metallic organic backbone
The enzyme of root peroxidase specific ionization has the performance (corresponding diagram 10C) of better resistance to tetrahydrofuran, dimethyl sulfoxide (DMSO) and acetone；
And C3, the multi-stage porous zirconium-based metallic organic backbone of horseradish peroxidase will be loaded in HEPES buffer solutions to adjacent benzene
Diamines is catalyzed, and is washed out being catalyzed again, and Xun Huan several times, to test the cycle performance of immobilised enzymes, fix by the results show
Horseradish peroxidase Xun Huan on multi-stage porous zirconium-based metallic organic backbone still keeps about 75% work after being catalyzed five times
Property (corresponding diagram 10D).
Biological big point can be effectively adsorbed in the adjustable grading-hole zirconium-based metallic organic backbone of aperture parameters according to the present invention
Son, and can efficient enzymatic be carried out with immobilised enzymes molecule.Experiment is loaded to cytochrome c and shows that aperture of the invention is joined
The useful load of the adjustable multi-stage porous metal organic framework of number can reach 214mg/g, while to the fixed amount of horseradish peroxidase
It can reach 94mg/g.Enzymatic experiment shows that the adjustable multi-stage porous zirconium-based metallic organic backbone of aperture parameters of the invention is multistage
After fixed horseradish peroxidase, efficient catalytic capability, good circulation ability and outstanding are shown to o-phenylenediamine
Anti- organic solvent ability.Preparation process according to the present invention is simple and efficient, reproducible, passes through simple etch step
Stable hierarchical porous structure is obtained, realizes the absorption to large biological molecule and effective fixation of enzyme molecule.
In short, preparation in accordance with the present invention, during monocarboxylic acid etches and to form multi-stage porous, partial pore quilt
It remains, this multi-stage porous metal organic framework caused is steady with the chemical stability and heat similar with former porous skeleton
It is qualitative.Nano material according to the present invention, metal organic framework effectively can adsorb and fix large biological molecule, in absorption point
Good application prospect is shown from, enzyme immobilizatio and catalytic field.Application according to the present invention, multistage mesoporous metal are organic
The fixed horseradish peroxidase of skeleton has good cycle performance and anti-organic solvent properties.
Description of the drawings
Fig. 1 is the technique of the preparation method of the adjustable multi-stage porous metal organic framework nano material in aperture according to the present invention
Flow chart；
Fig. 2 is the XRD spectrum of 1 obtained each multi-stage porous metal organic framework nano material according to an embodiment of the invention；
Fig. 3 A are that the nitrogen of 1 obtained each multi-stage porous metal organic framework nano material according to an embodiment of the invention is inhaled
Attached-desorption figure；
Fig. 3 B are the pore-size distributions of 1 obtained each multi-stage porous metal organic framework nano material according to an embodiment of the invention
Figure；
Fig. 4 a are the according to an embodiment of the invention 1 multi-stage porous metal organic framework nanometer materials etched using formic acid
The scanning electron microscope (SEM) photograph of material；
Fig. 4 b are the partial enlarged views of Fig. 4 a；
Fig. 4 c are the according to an embodiment of the invention 1 multi-stage porous metal organic framework nanometer materials etched using acetic acid
The scanning electron microscope (SEM) photograph of material；
Fig. 4 d are the partial enlarged views of Fig. 4 c；
Fig. 4 e are the according to an embodiment of the invention 1 multi-stage porous metal organic framework nanometer materials etched using propionic acid
The scanning electron microscope (SEM) photograph of material；
Fig. 4 f are the partial enlarged views of Fig. 4 e；
Fig. 4 g are the multi-stage porous metal organic framework nanometer materials according to an embodiment of the invention etched using butyric acid
The scanning electron microscope (SEM) photograph of material；
Fig. 4 h are the partial enlarged views of Fig. 4 g；
Fig. 5 A are that the nitrogen of 2 obtained each multi-stage porous metal organic framework nano materials according to an embodiment of the invention is inhaled
Attached-desorption figure；
Fig. 5 B are the pore-size distributions of 2 obtained each multi-stage porous metal organic framework nano materials according to an embodiment of the invention
Figure；
Fig. 6 A are that the nitrogen of 3 obtained each multi-stage porous metal organic framework nano materials according to an embodiment of the invention is inhaled
Attached-desorption figure；
Fig. 6 B are the pore-size distributions of 3 obtained each multi-stage porous metal organic framework nano materials according to an embodiment of the invention
Figure；
Fig. 7 a be according to an embodiment of the invention 3 the multistage mesoporous metal that etches of the propionic acid using 0.4mol/L it is organic
The transmission electron microscope photo of skeleton nano material；
Fig. 7 b be according to an embodiment of the invention 3 the multistage mesoporous metal that etches of the propionic acid using 0.8mol/L it is organic
The transmission electron microscope photo of skeleton nano material；
Fig. 7 c be according to an embodiment of the invention 3 the multistage mesoporous metal that etches of the propionic acid using 1.6mol/L it is organic
The transmission electron microscope photo of skeleton nano material；
Fig. 7 d be according to an embodiment of the invention 3 the multistage mesoporous metal that etches of the propionic acid using 3.2mol/L it is organic
The transmission electron microscope photo of skeleton nano material；
Fig. 7 e be according to an embodiment of the invention 3 the multistage mesoporous metal that etches of the propionic acid using 4.8mol/L it is organic
The transmission electron microscope photo of skeleton nano material；
Fig. 7 f be according to an embodiment of the invention 3 the multistage mesoporous metal that etches of the propionic acid using 5.6mol/L it is organic
The transmission electron microscope photo of skeleton nano material；
Fig. 8 A are that the nitrogen of 4 obtained each multi-stage porous metal organic framework nano materials according to an embodiment of the invention is inhaled
Attached-desorption figure；
Fig. 8 B are the pore-size distributions of 4 obtained each multi-stage porous metal organic framework nano materials according to an embodiment of the invention
Figure；
Fig. 9 a are the according to an embodiment of the invention 1 obtained micropore zirconium-based metallic organic backbone (micro-UiO- of step b
66) transmission electron microscope photo；
Fig. 9 b are the multi-stage porous metal organic framework nano materials etched at 25 DEG C of according to an embodiment of the invention 4
Transmission electron microscope photo；
Fig. 9 c are the multi-stage porous metal organic framework nano materials etched at 60 DEG C of according to an embodiment of the invention 4
Transmission electron microscope photo；
Fig. 9 d are the multi-stage porous metal organic framework nanometer materials etched at 100 DEG C of according to an embodiment of the invention 4
The transmission electron microscope photo of material；
Fig. 9 e are the multi-stage porous metal organic framework nanometer materials etched at 140 DEG C of according to an embodiment of the invention 4
The transmission electron microscope photo of material；
Fig. 9 f are the multi-stage porous metal organic framework nanometer materials etched at 180 DEG C of according to an embodiment of the invention 4
The transmission electron microscope photo of material；
Figure 10 A are the multi-stage porous metal organic framework nanometer materials etched at 180 DEG C of according to an embodiment of the invention 4
The UV-visible absorption spectrum of the absorption horseradish peroxidase of material；
Figure 10 B are the multi-stage porous metal organic framework nanometer materials etched at 180 DEG C of according to an embodiment of the invention 4
The immobilised enzymes of material is to the catalytic effect comparison diagram of o-phenylenediamine；
Figure 10 C are the multi-stage porous metal organic framework nanometer materials etched at 180 DEG C of according to an embodiment of the invention 4
The anti-organic solvent properties test of the immobilised enzymes of material；
Figure 10 D are the multi-stage porous metal organic framework nanometer materials etched at 180 DEG C of according to an embodiment of the invention 4
The cycle performance test of the immobilised enzymes of material.
Specific embodiment
Below in conjunction with the accompanying drawings, presently preferred embodiments of the present invention is provided, and is described in detail.
In the present invention, MOF refers to metal organic framework (Metal Organic Framework)；Micro is referred to
Micropore (microporous)；UiO-66 refers to the title of MOF, and university's name according to where synthesizing the MOF for the first time is got,
Wherein, UiO is the english abbreviation of Univ Oslo Norway, and 66 be the 66th metal organic framework of university synthesis.
Embodiment 1
As shown in Figure 1, at ambient temperature,
A. 4 mMs of zirconium chloride is dissolved in 72mlN, in N dimethyl amide (DMF), then adds in 80 mMs
Benzoic acid do organic ligand, terephthalic acid (TPA) and 660 microlitres of concentrated hydrochloric acid (mass fraction 37%), ultrasound are added in after dissolving
When standing 24 is small in 120 DEG C of baking ovens after 30min；
B. the material centrifugation of room temperature is will be cooled to, is washed three times with DMF, is scattered in acetone and replaces DMF, replaced three days,
It is every 12 it is small when change an acetone.Then micropore zirconium-based metallic organic backbone (micro-UiO- is obtained when 100 DEG C of vacuum drying 24 are small
66)；
C., 100mg micropore zirconium-based metallic organic backbones (micro-UiO-66) are dispersed in the different unitary carboxylics of 1.6mol/L
In sour (formic acid FA, acetic acid AA, propionic acid PA and butyric acid BA) solution, 100 DEG C stand 6 it is small when after, water and ethyl alcohol are respectively washed several times, 100
It is DEG C dry 24 it is small when obtain the multi-stage porous metal organic framework nano material that different monocarboxylic acids etch.
Fig. 2 is the XRD spectrum of each multi-stage porous metal organic framework nano material obtained according to the present embodiment, all multistages
The Bragg diffraction peak of mesoporous metal organic backbone nano material is consistent with the UiO-66 simulated, illustrates to successfully synthesize by not
With the multi-stage porous metal organic framework nano material of acid etch.
Fig. 3 is N2 adsorption-desorption curve of each multi-stage porous metal organic framework nano material obtained according to the present embodiment
And pore-size distribution.It can be seen that the XRD diffraction maximums that have still had and than more uniform pore-size distribution after propionic acid and acetic acid etching.
Fig. 4 is the transmission electron microscope photo of each multi-stage porous metal organic framework nano material obtained according to the present embodiment, can
With the apparent presence for seeing multi-stage porous.The pore structure parameter of sample before and after each acid etch is given in the following table 1, thus may be used
Know, etching can be realized by formic acid FA, acetic acid AA, propionic acid PA and butyric acid BA to generate grading-hole.
Table 1
Embodiment 2
100mg micropore zirconium-based metallic organic backbones (micro-UiO-66) are dispersed in the propionic acid solution of 1.6mol/L,
After 100 DEG C stand different time, water and ethyl alcohol are respectively washed several times, and 100 DEG C of dryings 24 obtain the multi-stage porous gold of different etching time when small
Belong to organic backbone nano material.
Fig. 5 is N2 adsorption-desorption curve of each multi-stage porous metal organic framework nano material obtained according to the present embodiment
And pore-size distribution.It can be seen that 6 it is small when etching reach balance.The pore structure of different etching time sample is given in the following table 2
Parameter, it follows that etch period selection 6 is enough when small.
Table 2
Embodiment 3
Implementation and basic recipe are same as Example 2, and the concentration for only changing propionic acid is 0.4,0.8,3.2,4.8 and
5.6mol/L obtains obtaining the multi-stage porous metal organic framework nano material that adjusts of different propionate concentrations.
Fig. 6 is N2 adsorption-desorption curve of each multi-stage porous metal organic framework nano material obtained according to the present embodiment
And graph of pore diameter distribution, Fig. 7 are the transmission electricity of each multi-stage porous metal organic framework nano material obtained according to the present embodiment
Mirror photo.It can be found that mesoporous appearance at least needs the acid concentration of 0.8mol/L, and the model in the increase hole with acid concentration
It encloses increasing.The pore structure parameter of different acid concentration etching samples is given in the following table 3 it follows that monocarboxylic concentration
It should select in 0.8~5.6mol/L.
Table 3
Embodiment 4
Implementation and basic recipe are same as Example 2, and the temperature for only changing etching is 25,60,100,140,180
DEG C, obtain different temperatures adjust multi-stage porous metal organic framework nano material.
Fig. 8 is N2 adsorption-desorption curve of each multi-stage porous metal organic framework nano material obtained according to the present embodiment
And graph of pore diameter distribution, Fig. 9 are the transmission electron microscopes of each multi-stage porous metal organic framework nano material obtained according to the present embodiment
Photo.As the scope in the increase hole of sour temperature is increasing.The pore structure ginseng of different temperatures etching sample is given in the following table 4
Number, it follows that etching can occur at different temperatures, as temperature raises etching journey in the range of 25 DEG C~180 DEG C
Degree increases.
Table 4
Embodiment 5
180 DEG C of multi-stage porous metal organic framework nano materials etched of 4 gained of embodiment are scattered in horseradish peroxide
In HEPES (pH7.4) solution of compound enzyme (HRP), in 4 DEG C of stirrings for 24 hours, HRP-UiO-66-180 is obtained after centrifugation.Figure 10 A are
Adsorb the UV-visible absorption spectrum of horseradish peroxidase.It follows that the multi-stage porous zirconium-based metallic after 180 DEG C of etchings
Organic backbone has horseradish peroxidase an apparent adsorbance, and adsorbance is higher than 100 DEG C of etchings.
Embodiment 6
The HRP-UiO-66-180 of 5 gained of embodiment is scattered in HEPES (pH7.4) solution of o-phenylenediamine, is added in
The hydrogen peroxide of various concentration measures catalytic activity by monitoring absorbance change of the solution at 418nm.Figure 10 B are fixed
Change catalytic effect comparison diagram of the enzyme to o-phenylenediamine.It follows that the material after load enzyme has apparent catalytic activity, and not
For the cleaning solution of material all without enzymatic activity, this also illustrates that enzyme of load will not fall off after load and load.
Embodiment 7
The HRP-UiO-66-180 of 5 gained of embodiment is scattered in HEPES (pH7.4) solution of o-phenylenediamine, is added in
Then the organic solvent of equal volume adds in the hydrogen peroxide of various concentration, by monitoring absorbance change of the solution at 418nm
Activity of the immobilized enzyme is measured, so as to the anti-organic solvent properties of being fixed enzyme.Figure 10 C are the anti-organic solvents of immobilised enzymes
Performance test.It follows that immobilised enzymes specific ionization enzyme has the energy of better anti-tetrahydrofuran, dimethyl sulfoxide (DMSO) and acetone
Power.
Embodiment 9
The HRP-UiO-66-180 of 5 gained of embodiment is scattered in HEPES (pH7.4) solution of o-phenylenediamine, is added in
The hydrogen peroxide of various concentration measures activity of the immobilized enzyme, Ran Houli by monitoring absorbance change of the solution at 418nm
The heart, as above method measures enzymatic activity, so Xun Huan five times again after being washed twice with HEPES solution.Figure 10 D are immobilised enzymes
Cycle performance test chart.It follows that the horseradish peroxidase Xun Huan being fixed on multi-stage porous zirconium-based metallic organic backbone is urged
About 75% activity is still kept after changing five times.
The present invention substitutes organic ligand to cause a large amount of organic ligands and metal according to suitable formula by monocarboxylic acid
The mechanism that cluster comes off constructs multi-stage porous zirconium-based metallic organic backbone.Wherein, it is dense by modulation monocarboxylic acid species, change acid
Degree, change acid etch time, change reaction temperature can effectively be adjusted the parameter of multi-stage porous；In addition, obtained multistage
Pore structure inherits the chemical stability and thermal stability of former microcellular structure.This hierarchical porous structure can adsorb biological big point
Son, being effectively fixed enzyme molecule, show good application prospect in the fields such as adsorbing separation and enzymatic.
It is above-described, it is only presently preferred embodiments of the present invention, is not limited to the scope of the present invention, of the invention is upper
Stating embodiment can also make a variety of changes.What i.e. every claims and description according to the present patent application were made
Simply, equivalent changes and modifications falls within the claims of patent of the present invention.The not detailed description of the present invention is
Routine techniques content.
Claims (10)
1. a kind of preparation method of the adjustable multi-stage porous metal organic framework nano material in aperture, which is characterized in that including as follows
Step：
S1, the synthetic microporous zirconium-based metallic of method that terephthalic acid (TPA) is passed through into solvent heat under the conditions of existing for conditioning agent with zirconates
Organic backbone, wherein, zirconates provides zirconium oxygen cluster as node, and terephthalic acid (TPA) is coordinated as connector and zirconium oxygen cluster from group
Dress forms three-dimensional porous crystalline framework；
S2, by micropore zirconium-based metallic organic backbone dry, micropore zirconium-based metallic activated after low boiling point solvent activation
Organic backbone；
The micropore zirconium-based metallic organic backbone of activation is dispersed at 25-180 DEG C in the monocarboxylic acid of 0.8-5.6mol/L by S3
Etching, obtains multi-stage porous metal organic framework nano material, wherein, monocarboxylic acid substitutes organic ligand and matches somebody with somebody with zirconium oxygen cluster
Position.
2. preparation method according to claim 1, which is characterized in that the zirconates for zirconium chloride, six water oxygen zirconium chlorides or
Zirconium nitrate.
3. preparation method according to claim 1, which is characterized in that the conditioning agent is benzoic acid.
4. preparation method according to claim 1, which is characterized in that the molar ratio of terephthalic acid (TPA), zirconates and conditioning agent
For 1：1：20.
5. preparation method according to claim 1, which is characterized in that step S1 is specially：By zirconium chloride, to benzene two
Formic acid dissolving forms the first solution in a solvent, and conditioning agent is added in the first solution and forms the second solution, inorganic acid is added in
The 3rd solution is formed in second solution, ultrasound obtains micropore zirconium-based metallic organic backbone after 120 DEG C of standings.
6. preparation method according to claim 5, which is characterized in that the solvent is N, and N dimethyl amide, which is
Concentrated hydrochloric acid.
7. preparation method according to claim 1, which is characterized in that step S2 is specially：Acetone soak micropore zirconium base
Metal organic framework.
8. preparation method according to claim 1, which is characterized in that the monocarboxylic acid is formic acid, acetic acid, propionic acid or fourth
Acid.
9. the adjustable multistage mesoporous metal in aperture that a kind of preparation method according to any one of claim 1-8 obtains is organic
Skeleton nano material, which is characterized in that the multi-stage porous metal organic framework nano material has meso-hole structure and microcellular structure.
10. a kind of multi-stage porous metal organic framework applications to nanostructures according to claim 9, which is characterized in that should
Multi-stage porous metal organic framework nano material is used to adsorb large biological molecule cytochrome c and immobilized HRP.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585856A (en) * | 2008-05-23 | 2009-11-25 | 安徽大学 | With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation |
| CN103111262A (en) * | 2013-01-31 | 2013-05-22 | 北京大学 | Porous material of metal-organic framework and preparation method of material |
| CN107365759A (en) * | 2017-09-07 | 2017-11-21 | 陕西师范大学 | A kind of high stable multi-stage porous Zr MOF immobilized enzyme reactors and its application |
-
2017
- 2017-12-22 CN CN201711403464.7A patent/CN108114699B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585856A (en) * | 2008-05-23 | 2009-11-25 | 安徽大学 | With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation |
| CN103111262A (en) * | 2013-01-31 | 2013-05-22 | 北京大学 | Porous material of metal-organic framework and preparation method of material |
| CN107365759A (en) * | 2017-09-07 | 2017-11-21 | 陕西师范大学 | A kind of high stable multi-stage porous Zr MOF immobilized enzyme reactors and its application |
Non-Patent Citations (1)
| Title |
|---|
| JARED B. DECOSTE ET AL.: "Hierarchical Pore Development by Plasma Etching of Zr-Based Metal–Organic Frameworks", 《CHEM. EUR. J.》 * |
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