CN107857886A - A kind of Zr MOF preparation method - Google Patents
A kind of Zr MOF preparation method Download PDFInfo
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- CN107857886A CN107857886A CN201711161985.6A CN201711161985A CN107857886A CN 107857886 A CN107857886 A CN 107857886A CN 201711161985 A CN201711161985 A CN 201711161985A CN 107857886 A CN107857886 A CN 107857886A
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- mof
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a kind of method for preparing Zr MOF, belong to metal-organic framework material preparing technical field.The present invention uses ionic liquid as solvent, adds appropriate conditioning agent, and Zr MOF can be quickly prepared under the conditions of being stirred at room temperature.Preparation method of the present invention has the advantages that simple for process, reaction condition is gentle, green non-pollution.
Description
Technical field
The present invention relates to a kind of method for preparing Zr-MOF, belong to metal-organic framework material preparing technical field.
Background technology
2008, Lillerud groups reported a kind of preparation method of the Zr-MOF with ultrastability, are labeled as
UiO-66, chemical formula Zr6O4(OH)4(CO2)12, framework caves in temperature higher than 500 DEG C, and with good water-resistance and resists
Acid-base property.Its stability is octahedra from the inorganic metal construction unit Zr6O4 (OH) 4 of high degree of symmetry, and the octahedron
Strong interaction between core and part carboxylate oxygen atoms.Thus, Zr-MOF preparation and its application, causes researcher pole
Big interest.But the main or traditional solvent-thermal method of the Zr-MOF reported at present preparation method, it usually needs be heated to 120
DEG C, more than 24h is reacted, commonly uses DMF (DMF), the organic solvent conduct such as N, N- diethylformamides (DEF)
Solvent.Zr-MOF is prepared with water substitution organic solvent and also has been reported that not only reaction temperature is higher, and many functionalization is organic
Solubility of the part in water is limited, is difficult to prepare the Zr-MOF of various different structures.Therefore, development room temperature is quickly prepared
Zr-MOF novel method has great importance.
The premium properties of ionic liquid makes it show great advantage in terms of MOF preparations, at present in ionic liquid
A variety of MOF materials, such as Zn-MOF, Fe-MOF, Al-MOF etc. are made in body.Although ionic liquid, which prepares MOF materials, to be had a lot
Advantage, but because its viscosity is more much bigger than organic solvent during room temperature, therefore typically using the hot method of ionic liquid, it is necessary to be heated to
Certain temperature is reacted and (is generally greater than 100 DEG C).There is no still ionic liquid under room temperature condition to prepare Zr- as solvent at present
MOF report.
The content of the invention
The invention aims to solve existing method to prepare high Zr-MOF reaction temperatures, reaction time length, solvent for use
For organic solvent the problems such as, and provide the green method that a kind of room temperature quickly prepares Zr-MOF.
Technical scheme comprises the following steps：
1. metal zirconates and organic ligand are added in ionic liquid, appropriate conditioning agent is added, it is stirred at room temperature 0.5~
After 24 hours, add ethanol and continue stirring a period of time, centrifuge products therefrom, obtain Zr-MOF.
2. a kind of method for preparing Zr-MOF of the present invention, ionic liquid used is 1- hexyl -3- methylimidazole villaumites, 1-
Octyl group -3- methylimidazole villaumites, 1- decyl -3- methylimidazole villaumites, 1- hexyl -3- methylimidazoles bromide, 1- hexyl -3- methyl
One or both of iodonium imidazolide salts, 1- hexyl -2,3- methylimidazole villaumites mix
3. a kind of method for preparing Zr-MOF of the present invention, metal zirconates used is zirconium chloride, zirconium sulfate, eight hydration dichloros
One kind in oxygen zirconium, zirconium-n-propylate, tetraethoxy zirconium, bis cyclopentadienyl zirconium dichloride.
4. a kind of method for preparing Zr-MOF of the present invention, organic ligand used is terephthalic acid (TPA), 2- amino to benzene two
Formic acid, 2- nitroterephthalics, 2- bromo terephthalic acids, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, 4,4- biphenyl dicarboxylic acids, 2,2- di- pyrroles
One kind in pyridine -5,5- dioctyl phthalate, 2,5- thiophene dicarboxylic acids, trimesic acid, four (to carboxyl phenyl) porphyrins.
5. a kind of method for preparing Zr-MOF of the present invention, conditioning agent used is in formic acid, glacial acetic acid, benzoic acid, hydrochloric acid
One kind.
6. the mol ratio of a kind of method for preparing Zr-MOF of the present invention, metal zirconates and organic ligand is 4:1~1:4, it is excellent
Elect 2 as:1~1:2.
7. the mol ratio of a kind of method for preparing Zr-MOF of the present invention, metal zirconates and conditioning agent is 1:50~1:200,
Preferably 1:100~1:150.
8. a kind of method for preparing Zr-MOF of the present invention, the time of reaction is 0.5~24 hour.Preferably 1-12 hours.
The present invention uses ionic liquid to solve the pollution problem of MOF preparation process organic solvents for solvent, overcome simultaneously
This difficult problem of organic ligand dissolving during using water as solvent.The quick of Zr-MOF materials can be realized at ambient temperature
Prepare.
Brief description of the drawings
Fig. 1 is the XRD of Zr-MOF prepared by embodiment 1-5.
Fig. 2 is the XRD of Zr-MOF prepared by embodiment 6-10.
Fig. 3 is the XRD of Zr-MOF prepared by embodiment 11.
Fig. 4 is the transmission electron microscope picture of Zr-MOF prepared by embodiment 1.
Embodiment
The embodiment of the present invention is described further below in conjunction with the accompanying drawings.
Embodiment 1
Weigh 0.4mmol zirconium chlorides, 0.4mmol terephthalic acid (TPA)s are matched somebody with somebody in 10ml 1- octyl group -3- methylimidazole villaumites
Into solution, 3ml glacial acetic acid is charged with, is stirred 24 hours at room temperature.Add ethanol in proper amount washing products therefrom, centrifugation point
From vacuum drying products therefrom is white solid powder.
Embodiment 2
Weigh 0.4mmol zirconium chlorides, 0.4mmol terephthalic acid (TPA)s are matched somebody with somebody in 10ml 1- octyl group -3- methylimidazole villaumites
Into solution, 3ml glacial acetic acid is charged with, is stirred 2 hours at room temperature.Ethanol in proper amount washing products therefrom is added, is centrifuged,
Vacuum drying products therefrom is white solid powder.
Embodiment 3
Weigh 0.4mmol zirconium chlorides, 0.4mmol terephthalic acid (TPA)s are matched somebody with somebody in 10ml 1- octyl group -3- methylimidazole villaumites
Into solution, 6ml glacial acetic acid is charged with, is stirred 24 hours at room temperature.Add ethanol in proper amount washing products therefrom, centrifugation point
From vacuum drying products therefrom is white solid powder.
Embodiment 4
Weigh 0.4mmol zirconium chlorides, 0.4mmol terephthalic acid (TPA)s are matched somebody with somebody in 10ml 1- octyl group -3- methylimidazole bromides
Into solution, 3ml glacial acetic acid is charged with, is stirred 24 hours at room temperature.Add ethanol in proper amount washing products therefrom, centrifugation point
From vacuum drying products therefrom is white solid powder.
Embodiment 5
0.2mmol zirconium-n-propylates, 0.4mmol terephthalic acid (TPA)s are weighed in 10ml 1- octyl group -3- methylimidazole villaumites
Wiring solution-forming, 3ml glacial acetic acid is charged with, stirred 24 hours at room temperature.Add ethanol in proper amount washing products therefrom, centrifugation point
From vacuum drying products therefrom is white solid powder.
Embodiment 6
0.4mmol zirconium chlorides, 0.4mmol 2- nitroterephthalics are weighed in 10ml 1- octyl group -3- methylimidazole chlorine
Wiring solution-forming in salt, 3ml glacial acetic acid is charged with, stirred 24 hours at room temperature.Ethanol in proper amount washing products therefrom is added, from
The heart separates, and vacuum drying products therefrom is white solid powder, UiO-66-NO2。
Embodiment 7
0.4mmol zirconium chlorides, 0.4mmol 2- hydroxyterephthalic acids are weighed in 10ml 1- octyl group -3- methylimidazole chlorine
Wiring solution-forming in salt, 3ml glacial acetic acid is charged with, stirred 24 hours at room temperature.Ethanol in proper amount washing products therefrom is added, from
The heart separates, and vacuum drying products therefrom is white solid powder, UiO-66-HO.
Embodiment 8
0.4mmol zirconium chlorides, 0.4mmol 2- bromo terephthalic acids are weighed in 10ml 1- octyl group -3- methylimidazole villaumites
Middle wiring solution-forming, 3ml glacial acetic acid is charged with, stirred 24 hours at room temperature.Add ethanol in proper amount washing products therefrom, centrifugation
Separation, vacuum drying products therefrom are white solid powder, UiO-66-Br.
Embodiment 9
0.4mmol zirconium chlorides, 0.4mmol 2- amino terephthalic acid (TPA)s are weighed in 10ml 1- octyl group -3- methylimidazole chlorine
Wiring solution-forming in salt, 3ml glacial acetic acid is charged with, stirred 24 hours at room temperature.Ethanol in proper amount washing products therefrom is added, from
The heart separates, and vacuum drying products therefrom is white solid powder, UiO-66-NH2。
Embodiment 10
0.4mmol zirconium chlorides, 0.4mmol 1,4- naphthalenedicarboxylic acids are weighed in 10ml 1- octyl group -3- methylimidazole villaumites
Wiring solution-forming, 3ml glacial acetic acid is charged with, stirred 24 hours at room temperature.Add ethanol in proper amount washing products therefrom, centrifugation point
It is white solid powder from, vacuum drying products therefrom, UiO-66-Ar.
Embodiment 11
0.4mmol zirconium chlorides, (to the carboxyl phenyl) porphyrins of 0.4mmol tetra- are weighed in 10ml 1- octyl group -3- methylimidazoles
Wiring solution-forming in villaumite, 3ml glacial acetic acid is charged with, stirred 24 hours at room temperature.Ethanol in proper amount washing products therefrom is added,
Centrifuge, vacuum drying products therefrom is white solid powder, PCN-224.
Claims (3)
- A kind of 1. method for preparing Zr-MOF, it is characterised in that：Metal zirconates and organic ligand are added in ionic liquid, add appropriate conditioning agent, is stirred at room temperature 0.5~24 hour Afterwards, add ethanol and continue stirring a period of time, centrifuge products therefrom, obtain Zr-MOF.
- A kind of 2. method for preparing Zr-MOF according to claim 1, it is characterised in that：Ionic liquid used be 1- oneself Base -3- methylimidazole villaumites, 1- octyl group -3- methylimidazole villaumites, 1- decyl -3- methylimidazole villaumites, 1- hexyl -3- methyl miaows One or both of azoles bromide, 1- hexyl -3- methylimidazoles salt compounded of iodine, 1- hexyl -2,3- methylimidazole villaumites mix；It is used Metal zirconates be zirconium chloride, zirconium sulfate, eight hydration zirconium oxychlorides, zirconium-n-propylate, tetraethoxy zirconium, one in bis cyclopentadienyl zirconium dichloride Kind；Organic ligand used is terephthalic acid (TPA), 2- amino terephthalic acid (TPA), 2- nitroterephthalics, 2- bromine terephthaldehydes Acid, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, 4,4- biphenyl dicarboxylic acids, 2,2- bipyridines -5,5- dioctyl phthalate, 2,5- thiophene dicarboxylic acids, equal benzene three One kind in formic acid, four (to carboxyl phenyl) porphyrins；Conditioning agent used is one in formic acid, glacial acetic acid, benzoic acid, hydrochloric acid Kind.
- A kind of 3. method for preparing Zr-MOF according to claim 1, it is characterised in that：Metal zirconates and organic ligand Mol ratio is 4:1~1:4；The mol ratio of metal zirconates and conditioning agent is 1:50~1:200..
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816287A (en) * | 2018-05-23 | 2018-11-16 | 福州大学 | Uio-66 immobilized Carboxyl-functional Ionic Liquid composite material and its preparation and application in situ |
| CN108872165A (en) * | 2018-04-02 | 2018-11-23 | 浙江大学 | A kind of mycotoxin colorimetric sensing method based on fluorescence metal organic framework materials |
| CN108912340A (en) * | 2018-07-20 | 2018-11-30 | 河南中烟工业有限责任公司 | A kind of humectation type cigarette paper and preparation method thereof |
| CN109056421A (en) * | 2018-07-20 | 2018-12-21 | 河南中烟工业有限责任公司 | A kind of humectation type internal lining paper and preparation method thereof |
| CN109232903A (en) * | 2018-09-04 | 2019-01-18 | 江南大学 | A kind of environment-friendly preparation method thereof of metal-organic framework materials |
| CN109338816A (en) * | 2018-11-21 | 2019-02-15 | 无锡高强特种纺织有限公司 | A kind of wear-resisting sound-proof wallpaper and preparation method thereof |
| CN109876776A (en) * | 2019-02-02 | 2019-06-14 | 北京建筑大学 | Indium base MOF micro-nano powder and its room temperature preparation method and application |
| CN109959686A (en) * | 2019-04-01 | 2019-07-02 | 浙江大学 | A kind of hydrogen peroxide electrode and preparation method thereof |
| CN109970985A (en) * | 2019-03-15 | 2019-07-05 | 中国石油大学(华东) | A kind of method of room temperature synthesis metal-organic framework material PCN-224 |
| CN110554011A (en) * | 2019-08-22 | 2019-12-10 | 武汉大学 | visual water fluorescence microsensor based on dual-response lanthanide MOF, water determination pipe device, water visualization determination device and application thereof |
| CN110618224A (en) * | 2019-08-06 | 2019-12-27 | 华东师范大学 | [ H ]2Nmim][NTf2]@ UiO-66-Br nano composite material and application thereof |
| CN110684201A (en) * | 2018-07-05 | 2020-01-14 | 丰田自动车株式会社 | Method for producing coordinatively unsaturated metal-organic structure, and coordinatively unsaturated metal-organic structure |
| CN111359668A (en) * | 2020-04-23 | 2020-07-03 | 浙江大学 | Preparation method of metal organic framework single-site catalyst for simulating peroxidase |
| CN111690148A (en) * | 2020-06-22 | 2020-09-22 | 江南大学 | Green preparation method of two-dimensional metal-organic framework material |
| CN112680601A (en) * | 2020-12-02 | 2021-04-20 | 昆山鸿福泰环保科技有限公司 | Method for recovering silver and gold from silver and gold-containing anode slime |
| CN115160590A (en) * | 2022-08-22 | 2022-10-11 | 北京航空航天大学 | Preparation method of surface enhanced Raman spectrum substrate with bimetallic metal organic framework |
| CN116375593A (en) * | 2023-06-06 | 2023-07-04 | 吉林省卓材新研科技有限公司 | Metal organic frame material for iodine adsorption, ligand and application |
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Cited By (26)
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| CN108872165A (en) * | 2018-04-02 | 2018-11-23 | 浙江大学 | A kind of mycotoxin colorimetric sensing method based on fluorescence metal organic framework materials |
| CN108816287A (en) * | 2018-05-23 | 2018-11-16 | 福州大学 | Uio-66 immobilized Carboxyl-functional Ionic Liquid composite material and its preparation and application in situ |
| CN108816287B (en) * | 2018-05-23 | 2020-12-25 | 福州大学 | Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof |
| CN110684201B (en) * | 2018-07-05 | 2022-04-19 | 丰田自动车株式会社 | Method for producing coordinatively unsaturated metal-organic structure, and coordinatively unsaturated metal-organic structure |
| CN110684201A (en) * | 2018-07-05 | 2020-01-14 | 丰田自动车株式会社 | Method for producing coordinatively unsaturated metal-organic structure, and coordinatively unsaturated metal-organic structure |
| CN108912340A (en) * | 2018-07-20 | 2018-11-30 | 河南中烟工业有限责任公司 | A kind of humectation type cigarette paper and preparation method thereof |
| CN109056421A (en) * | 2018-07-20 | 2018-12-21 | 河南中烟工业有限责任公司 | A kind of humectation type internal lining paper and preparation method thereof |
| CN108912340B (en) * | 2018-07-20 | 2021-04-20 | 河南中烟工业有限责任公司 | Moisture-retaining cigarette paper and preparation method thereof |
| CN109232903B (en) * | 2018-09-04 | 2020-09-29 | 江南大学 | Green preparation method of metal-organic framework material |
| CN109232903A (en) * | 2018-09-04 | 2019-01-18 | 江南大学 | A kind of environment-friendly preparation method thereof of metal-organic framework materials |
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| CN109876776A (en) * | 2019-02-02 | 2019-06-14 | 北京建筑大学 | Indium base MOF micro-nano powder and its room temperature preparation method and application |
| CN109876776B (en) * | 2019-02-02 | 2022-04-15 | 北京建筑大学 | Indium-based MOF micro-nano powder and room-temperature preparation method and application thereof |
| CN109970985A (en) * | 2019-03-15 | 2019-07-05 | 中国石油大学(华东) | A kind of method of room temperature synthesis metal-organic framework material PCN-224 |
| CN109959686A (en) * | 2019-04-01 | 2019-07-02 | 浙江大学 | A kind of hydrogen peroxide electrode and preparation method thereof |
| CN110618224B (en) * | 2019-08-06 | 2021-11-19 | 华东师范大学 | [ H ]2Nmim][NTf2]@ UiO-66-Br nano composite material and application thereof |
| CN110618224A (en) * | 2019-08-06 | 2019-12-27 | 华东师范大学 | [ H ]2Nmim][NTf2]@ UiO-66-Br nano composite material and application thereof |
| CN110554011A (en) * | 2019-08-22 | 2019-12-10 | 武汉大学 | visual water fluorescence microsensor based on dual-response lanthanide MOF, water determination pipe device, water visualization determination device and application thereof |
| CN111359668A (en) * | 2020-04-23 | 2020-07-03 | 浙江大学 | Preparation method of metal organic framework single-site catalyst for simulating peroxidase |
| CN111690148A (en) * | 2020-06-22 | 2020-09-22 | 江南大学 | Green preparation method of two-dimensional metal-organic framework material |
| CN112680601A (en) * | 2020-12-02 | 2021-04-20 | 昆山鸿福泰环保科技有限公司 | Method for recovering silver and gold from silver and gold-containing anode slime |
| CN112680601B (en) * | 2020-12-02 | 2022-04-15 | 昆山鸿福泰环保科技有限公司 | Method for recovering silver and gold from silver and gold-containing anode slime |
| CN115160590A (en) * | 2022-08-22 | 2022-10-11 | 北京航空航天大学 | Preparation method of surface enhanced Raman spectrum substrate with bimetallic metal organic framework |
| CN116375593A (en) * | 2023-06-06 | 2023-07-04 | 吉林省卓材新研科技有限公司 | Metal organic frame material for iodine adsorption, ligand and application |
| CN116375593B (en) * | 2023-06-06 | 2023-10-20 | 吉林省卓材新研科技有限公司 | Metal organic frame material for iodine adsorption, ligand and application |
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