CN109400890A - A kind of preparation method of multi-stage porous metal-organic framework materials - Google Patents
A kind of preparation method of multi-stage porous metal-organic framework materials Download PDFInfo
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- CN109400890A CN109400890A CN201710711981.4A CN201710711981A CN109400890A CN 109400890 A CN109400890 A CN 109400890A CN 201710711981 A CN201710711981 A CN 201710711981A CN 109400890 A CN109400890 A CN 109400890A
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Abstract
The present invention discloses a kind of preparation method of multi-stage porous metal-organic framework materials, it is characterised in that including the following steps: metal zirconates and omega-dicarboxylic acids organic ligand are added in aprotic polar solvent, is stirred at room temperature to solid and all dissolves to obtain solution one；Mono carboxylic organic acid is added into solution one, stirs evenly；Alkaline solution adjusts pH to 2.0~7.0, then starts to react, and control reaction temperature is 25~300 DEG C, and the reaction time is 5min~48h；It is above-mentioned to be centrifuged, wash and dry and to obtain target product after reaction.Using method provided by the invention, by can successfully obtain the little crystal grain zirconium base MOFs material of Nano grade to metal ion and organic control with nucleation and crystalline rate.Little crystal grain is easy to contact with each other, accumulate and form permanent meso-hole structure between crystal grain since surface can be higher.This method synthesis step is simple and easy, does not need that the higher template of price is added, is not necessarily to stripper plate, simplifies synthesis step.
Description
Technical field
The present invention relates to metal-organic framework materials, and in particular to a kind of preparation side of multi-stage porous metal-organic framework materials
Method.
Background technique
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) are as a kind of emerging porous material
The complex of periodic structure is self-assembly of by coordinate bond by inorganic metal center and organic ligand.With it is traditional
The porous materials such as molecular sieve, active carbon, silica gel are compared, and metal-organic framework materials have bigger specific surface area and porosity,
Especially by the modification of ligand can be obtained aperture, polarity etc. can modulation flexible molecule skeleton so that organometallic skeletal material
Material is widely used in fields such as catalysis, separation.Although MOFs material structure and aspect of performance show traditional material without
The advantage of method analogy, but heavy industrialization application not yet at present, main there are two reasons: the stabilization of first, MOFs material
Property is not high；Second, reported MOFs materials most is poromerics (aperture < 2nm), this results in the resistance in molecule disengaging duct
Power is larger, and the energy consumption of operating process is higher.In order to improve the stability of MOFs material, researcher from metal ion, ligand with
And coordination mode sets out and conducts in-depth research, and constantly synthesizes the preferable MOFs material of stability.Such as UiO-66, it by
Zirconium octahedron oxygen cluster Zr6O4(OH)4A cube space three-dimensional structure for close heap form is constituted with 12 terephthalic acid (TPA) coordinations, is had
There is the diameter to be respectivelyOctahedra cage and tetrahedron cage, and be by diameterTriangular orifice mutually interconnect
It is logical.Since the more other metals of Zr-O coordinate bond that the metal zirconium and oxygen atom that are in the 4th subgroup are formed are more stable, in addition, its
The reason of ligancy is up to 12, these two aspects makes UiO-66 have good thermal stability, chemical stability and mechanically stable
Property, while specific surface area with higher and Kong Rong.However, the microcellular structure of UiO-66 limits further applying for it.For
Reduce diffusional resistance of the molecule in micropore canals, synthesis has micropore-mesopore structure multi-stage porous MOF material as changing simultaneously
The effective way of kind micropore MOFs mass-transfer efficiency.
Currently, the synthesis in relation to multi-stage porous MOFs mostly uses template, i.e., ionic table is added in MOFs synthesis process
The substances such as face activating agent, biology base template or polymer blocks compound, so that in MOF intra-die due to template micella
Presence generate it is a certain proportion of mesoporous.However, above method step is complicated, reagent is costly, while using this method meeting
Lead to micropore specific surface and the decline of Kong Rong, to reduce the adsorption capacity of material itself.
Summary of the invention
The problem to be solved in the present invention is that the zirconium-based metallic of the method preparation of existing synthesis multi-stage porous MOFs material has
The micropore specific surface of machine framework material and hole appearance are lower, and synthesis step is complicated, at high cost.
To solve the above-mentioned problems, the present invention discloses a kind of preparation method of multi-stage porous metal-organic framework materials, specifically
Including the following steps:
(1) metal zirconates and dicarboxylic acids organic ligand are added in aprotic polar solvent, are stirred at room temperature to solid
All dissolve to obtain solution one；
(2) mono carboxylic organic acid is added into solution one, stirs evenly to obtain solution two；
(3) alkaline solution is added dropwise into solution two and adjusts pH to 2.0~7.0, obtain solution three；
(4) control of solution three is reacted in 25-300 DEG C of temperature range, the reaction time is 5min~48h；
(5) above-mentioned to be centrifuged, wash and dry and to obtain target product after reaction.
Metal center source of the above-mentioned metal zirconates as framework material, dicarboxylic acids support as organic ligand and constitute space
3D extends.Alkalinity is added in the reaction system that aprotic polar solvent is formed in above-mentioned zirconium metal and omega-dicarboxylic acids organic ligand
Solution can speed up the formation of zirconium octahedron oxygen cluster, while promote the deprotonation process of dicarboxyl acid organic ligand, thus plus
Fast nucleation rate and crystalline rate are conducive to the generation of little crystal grain；But the process often will cause the generation of zirconium gel and lead
Product yield is caused to reduce, the present invention in step (2) by being added mono carboxylic organic acid, so that itself and dicarboxyl organic ligand shape
At the environment of competitive coordination, controllable zirconium ion hydrolyzes to form the rate of zirconium oxygen cluster, is that a kind of raising nucleation crystalline nucleation rate is same
The effective ways of Shi Wending reaction process.
In above-mentioned steps (1), metal zirconates is zirconium chloride, basic zirconium chloride, zirconyl nitrate, zirconium-n-butylate, zirconium-n-propylate
Or zirconium acetate；Omega-dicarboxylic acids organic ligand is terephthalic acid (TPA) or amino terephthalic acid (TPA)；Aprotic polar solvent is N, N- bis-
Methylformamide, n,N-dimethylacetamide, acetonitrile, dimethyl sulfoxide or 1,3- dimethyl-imidazol alkanone.
In step (2), the mono carboxylic organic acid of addition is any mixed of formic acid, acetic acid or benzoic acid one or more of them
It closes.
In step (3), the alkaline solution of dropwise addition is water soluble alkali solution, including sodium hydroxide, potassium hydroxide, barium hydroxide
Or ammonium hydroxide.
A kind of synthetic method of multi-stage porous metal-organic framework materials proposed by the present invention, metal zirconium in above-mentioned steps (1)
The molar ratio of salt and omega-dicarboxylic acids organic ligand is 0.1~2 ﹕ 1, and the molar ratio of metal zirconates and non-protonic polar solvent is 1 ﹕
10~2000.
The molar ratio of mono carboxylic organic acid and metal zirconates is 10~200 ﹕ 1, preferably 50~150 ﹕ in above-mentioned steps (2)
1.
Further, the molar ratio of metal zirconates and omega-dicarboxylic acids organic ligand is preferably 0.5~1 ﹕ in above-mentioned steps (1)
1, the molar ratio of metal zirconates and non-protonic polar solvent is preferably 1 ﹕ 500~1500.
A kind of preparation method of multi-stage porous metal-organic framework materials proposed by the present invention, above-mentioned steps (3) neutral and alkali are molten
The concentration of liquid is 0.01~1.0mol/L, preferably 0.1~0.5mol/L.
The preparation method of multi-stage porous metal-organic framework materials provided by the invention, reaction temperature is excellent in above-mentioned steps (4)
It is selected as 100~150 DEG C, the reaction time is 10~for 24 hours.
Compared with prior art, the beneficial effects of the present invention are: use method provided by the invention, by metal from
The control of son and organic ligand nucleation and crystalline rate, can successfully obtain the little crystal grain zirconium base MOFs material of Nano grade, from
And the mass-transfer efficiency for improving poromerics itself.Little crystal grain since surface can be higher, be easy to contact with each other, accumulate and crystal grain it
Between form permanent meso-hole structure.This method synthesis step is simple and easy, does not need that the higher template of price is added, is not necessarily to
Stripper plate simplifies synthesis step.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention and comparative example；
Fig. 2 is 77K nitrogen adsorption-desorption isotherm of the embodiment of the present invention and comparative example；
Fig. 3 is the graph of pore diameter distribution of the embodiment of the present invention and comparative example.
Specific embodiment
For a better understanding of the present invention, the present invention is further illustrated below with reference to embodiment.
Embodiment 1
By the ZrCl of 0.23mmol4It is added in the n,N-Dimethylformamide of 25mL with 0.23mmol terephthalic acid (TPA),
1mL acetic acid is added after being stirred at room temperature to solid all dissolution, stirs evenly, the sodium hydroxide solution for being 0.1mol/L with concentration
Adjusting reaction solution pH value is 5；Above-mentioned mixed liquor is moved in the reaction kettle with polytetrafluoroethyllining lining, reaction kettle, control are sealed
Reaction temperature processed is 100 DEG C, reaction time 10h；Target product UiO- is centrifuged, washs and dried and to obtain after reaction
66-1。
Embodiment 2
By the ZrOCl of 0.23mmol2·8H2O and 0.23mmol terephthalic acid (TPA) is added to the N of 15mL, N- dimethylacetamide
In amine, 0.5mL acetic acid, the sodium hydroxide solution tune for being 0.3mol/L with concentration is added after being stirred at room temperature to solid all dissolution
Saving reaction solution pH value is 6, is stirred evenly at room temperature；Above-mentioned mixed liquor is moved in the reaction kettle with polytetrafluoroethyllining lining,
Reaction kettle is sealed, control reaction temperature is 120 DEG C, reaction time 12h；It is centrifuged, washs and dries after reaction
Obtain target product UiO-66-2.
Embodiment 3
By the ZrCl of 0.23mmol4It is added in the DMF of 10mL, stirs at room temperature to solid with 0.46mmol terephthalic acid (TPA)
Body is added 1mL benzoic acid after all dissolving and stirs evenly, and then uses concentration to adjust for the sodium hydroxide solution of 0.5mol/L mixed
Closing liquid pH value is 6；Then above-mentioned mixed liquor is moved in the reaction kettle with polytetrafluoroethyllining lining, seals reaction kettle, control
Reaction temperature is 150 DEG C, and the reaction time is for 24 hours；Target product UiO- is centrifuged, washs and dried and to obtain after reaction
66-3。
Comparative example 1
By 0.23mmolZrCl4It is put into the reaction kettle with polytetrafluoroethyllining lining with 0.23mmol terephthalic acid (TPA),
The DMF of 25mL is added, is uniformly mixed, control reaction temperature is 120 DEG C, reaction time 12h；After reaction through centrifugation point
From, washing and dry target product UiO-66-0.
By Fig. 1 and Fig. 2 it is found that the sample grain size that Examples 1 to 3 obtains is substantially reduced compared with comparative example 1, absorption etc.
Warm line is also changed from I to IV type, apparent hysteresis loop is occurred, is shown that there are mesoporous for UiO-66-1~3 three sample.By Fig. 3
Graph of pore diameter distribution is, it is apparent that the sample UiO-66-0 of comparative example 1 only has micropore presence, and the sample of Examples 1 to 3 is not only deposited
In micropore, obviously there is mesoporous presence in 30nm or so, in conclusion obtaining using method provided by the invention with multi-stage porous knot
The UiO-66 of structure.
Above-described embodiment is only preferred embodiment, is not limited the embodiments.For the common of fields
For technical staff, other different forms of changes or modifications may be made based on the above description.It is all according to the present invention
Equivalent changes and modifications made by the content of claim all should be used as technology scope of the invention.
Claims (10)
1. a kind of preparation method of multi-stage porous metal-organic framework materials, it is characterised in that including the following steps:
(1) metal zirconates and dicarboxylic acids organic ligand are added in aprotic polar solvent, are stirred at room temperature to solid whole
Dissolve to obtain solution one；
(2) mono carboxylic organic acid is added into solution one, stirs evenly to obtain solution two；
(3) alkaline solution is added dropwise into solution two and adjusts pH to 2.0~7.0, obtain solution three；
(4) control of solution three is reacted in 25~300 DEG C of temperature ranges, the reaction time is 5min~48h；
(5) above-mentioned to be centrifuged, wash and dry and to obtain target product after reaction.
2. the preparation method of multi-stage porous metal-organic framework materials as described in claim 1, it is characterised in that the metal zirconium
Salt is zirconium chloride, basic zirconium chloride, zirconyl nitrate, zirconium-n-butylate, zirconium-n-propylate or zirconium acetate；Dicarboxylic acids organic ligand is to benzene
Dioctyl phthalate or amino terephthalic acid (TPA)；Aprotic polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, second
Nitrile, dimethyl sulfoxide or 1,3- dimethyl-imidazol alkanone.
3. the preparation method of multi-stage porous metal-organic framework materials as described in claim 1, it is characterised in that in step (2),
Mono carboxylic organic acid is any mixing of formic acid, acetic acid or benzoic acid one or more of them.
4. the preparation method of multi-stage porous metal-organic framework materials as described in claim 1, it is characterised in that in step (3),
The alkaline solution of dropwise addition is sodium hydroxide, potassium hydroxide, barium hydroxide or ammonium hydroxide.
5. the preparation method of multi-stage porous metal-organic framework materials as described in claim 1, it is characterised in that above-mentioned steps (1)
The molar ratio of middle metal zirconates and omega-dicarboxylic acids organic ligand is 0.1~2 ﹕ 1, and metal zirconates and non-protonic polar solvent rub
You are than being 1 ﹕ 10~2000.
6. the preparation method of multi-stage porous metal-organic framework materials as described in claim 1, it is characterised in that single in step (2)
The molar ratio of carboxylate organic acids and metal zirconates is 10~200 ﹕ 1.
7. the preparation method of multi-stage porous metal-organic framework materials as described in claim 1, it is characterised in that golden in step (1)
Belong to the molar ratio of zirconates and dicarboxylic acids organic ligand for 0.5~1 ﹕ 1, the molar ratio of metal zirconates and non-protonic polar solvent is
1 ﹕ 500~1500.
8. the preparation method of multi-stage porous metal-organic framework materials as described in claim 1, it is characterised in that alkali in step (2)
Property solution concentration be 0.01~1.0mol/L.
9. the preparation method of multi-stage porous metal-organic framework materials as described in claim 1, it is characterised in that alkali in step (2)
Property solution concentration be 0.1~0.5mol/L.
10. the preparation method of multi-stage porous metal-organic framework materials as described in claim 1, it is characterised in that in step (4)
Reaction temperature be 100~150 DEG C, the reaction time be 10~for 24 hours.
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| CN110065989A (en) * | 2019-06-04 | 2019-07-30 | 温州大学 | A method of utilizing organic dyestuff in the metal organic framework material UIO-67 derivative absorption water of microcellular structure |
| CN110256683A (en) * | 2019-04-19 | 2019-09-20 | 武汉理工大学 | A kind of preparation method and applications of hierarchical porous structure metal-organic framework materials |
| CN111359663A (en) * | 2020-02-19 | 2020-07-03 | 浙江工业大学 | Application of catalyst based on organic metal framework UiO-66 in cellulose hydrolysis |
| CN111686693A (en) * | 2019-03-15 | 2020-09-22 | 中国石油化工股份有限公司 | Hierarchical porous MOFs material and preparation method and application thereof |
| CN111690144A (en) * | 2019-03-15 | 2020-09-22 | 中国石油化工股份有限公司 | Hierarchical pore UiO-66 material and preparation method and application thereof |
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| CN113441114A (en) * | 2021-08-04 | 2021-09-28 | 辽宁大学 | Mixed metal MOF and preparation method and application thereof |
| CN115466402A (en) * | 2022-09-06 | 2022-12-13 | 蚌埠学院 | Metal-organic framework material UiO-66 and ultrasonic synthesis method and application thereof |
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