CN105218832A - A kind of metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu and preparation method thereof - Google Patents
A kind of metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu and preparation method thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 59
- 239000003446 ligand Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims description 24
- 239000013110 organic ligand Substances 0.000 claims abstract description 16
- GSFGPCMKUFKBSR-UHFFFAOYSA-N C(=O)(O)C1=C(C(=NC=C1)C1=CC=CC=C1)C(=O)O Chemical compound C(=O)(O)C1=C(C(=NC=C1)C1=CC=CC=C1)C(=O)O GSFGPCMKUFKBSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- NBEFMISJJNGCIZ-UHFFFAOYSA-N 3,5-dimethylbenzaldehyde Chemical compound CC1=CC(C)=CC(C=O)=C1 NBEFMISJJNGCIZ-UHFFFAOYSA-N 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000002178 crystalline material Substances 0.000 abstract description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- -1 3,5-dicarboxyl phenyl ring Chemical group 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Abstract
A kind of metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu and preparation method thereof, belongs to the technical field of crystalline material.Chemical structural formula [Cu
2(H
2o)
2(BCPIA)], H
4bCPIA is that organic ligand 4-(3,5-bis-carboxyphenyl)-2,6-is to dicarboxyl phenylpyridine.This metal-organic framework synthesize sealing condition under, organic ligand 4,4 ˊ, 4 "; 4 " ˊ-(Isosorbide-5-Nitrae-Ya benzene two (pyridine-4,2; 6-tri-replaces)) four phenylformic acid and zirconium chloride in DMF, obtain the crystal of metal-organic framework via thermal response.In gas adsorption and storage, there is potential application.
Description
Technical field
The invention belongs to the technical field of crystalline material, technology relates to metal-organic coordination polymer material, particularly a kind of metal-organic framework based on novel low symmetrical four tooth Carboxylic acid ligand Cu and preparation method thereof.
Background technology
As a kind of novel inorganic-organic hybrid porous material, metal-organic framework (metal-organicframeworks, MOFs) not only because its potential application in gas adsorption and storage, fluorescence, catalysis, electrochemistry etc., also receive researcher because it has charming structure and diversified topology configuration and pay close attention to widely.Metal-organic framework to be constructed by coordinate bond by metal ion or metal cluster and organic ligand and is formed.In the strategy constructing metal-organic framework, framework chemistry (reticularchemistry) is that one constructs strategy efficiently.The metal cluster constructing metal-organic framework is thought secondary construction unit (SBU) by framework chemistry.Under similar synthesis condition, often can obtain identical SBU, this makes the controlledly synthesis of metal-organic framework become possibility.
Except SBU, the part constructing metal-organic framework is important too.Construct in the part of metal-organic framework numerous, Carboxylic acid ligand is a class part of people's most study, and it is of a great variety, and coordination mode is varied.And great majority are high degree of symmetry for the synthesis of the Carboxylic acid ligand of metal-organic framework.Relatively less with the research of asymmetric Carboxylic acid ligand synthetic metals-organic backbone.Low symmetrical part is connected with SBUs, often can construct out the metal-organic framework of novel structure, shows different performances.
Summary of the invention
The object of the present invention is to provide the preparation method of the synthetic method of the low symmetrical Carboxylic acid ligand of a kind of novel four tooth and the metal-organic framework with its Cu constructed.
The novel four tooth Carboxylic acid ligands of one of the present invention, are characterised in that it belongs to low symmetrical part.In addition, this part center pyridine ring and participate in coordination 3,5-dicarboxyl phenyl ring between coplanar; Between the 4-carboxyl phenyl ring of the pyridine ring at part center and two other participation coordination, formed interfacial angle is 27.3 °.
Metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu of the present invention, it is characterized in that, chemical molecular formula is [Cu
2(H
2o)
2(BCPIA)], H
4bCPIA is that organic ligand 4-(3,5-bis-carboxyphenyl)-2,6-is to dicarboxyl phenylpyridine.
Connect from the angle of skeleton and construct, the crystalline structure of this metal-organic framework belongs to trigonal system, and spacer is R3m, and unit cell parameters is:
α=β=90 °, γ=120 °.
Each Cu in this metal-organic framework
2+ion with the coordination mode of quadrangular pyramid and an O atom from water molecules and four from the coordination of different ligands carbonyl atom O; Two Cu
2+ion is connected with the carboxyl on two O atoms from water molecules and four different ligands and constitutes classical double-core Cu and take turns that slurry type is secondary constructs cell S BU [Cu
2(H
2o)
2(COO)
4].Each part is with cis-suitable (syn-syn) bridging coordination mode and eight Cu
2+ion coordination.The structure of caged is there is in this metal-organic framework.12 SUBs and six BCPIA
4-part defines an octahedra cage, and octahedra cage inscribed sphere diameter is about
each octahedral cage is connected with eight octahedra cages of surrounding by sharing leg-of-mutton, constitutes three-dimensional framework material.If the SBU of the double-core Cu in this metal-organic framework and four tooth Asymmetry coordinations to be simplified to the node of four connections, so this metal-organic framework is simplified to one four net connected, its Shi Laifuli symbol (
symbol) be (6
48
2), belong to the topology of Nbo type.After removing guest molecule, the enterable pore volume of this metal-organic framework is 73.1%, and this numerical value is calculated according to crystal data by PLATON software.
Wherein organic ligand 4-(3,5-bis-carboxyphenyl)-2,6-is to dicarboxyl phenylpyridine (H
4bCPIA) chemical structural formula is
The synthetic method of the novel low symmetrical four tooth Carboxylic acid ligands of the present invention, comprises following two steps:
First be 3,5-dimethylbenzaldehyde NaOH, ethanol and ammonium acetate deposit in case with 4-methyl acetophenone reaction cyclization, obtain 4-(3,5-xylyl)-2,6-p-Xylol yl pyridines.
Secondly product previous step obtained obtains this low symmetrical four tooth Carboxylic acid ligands through potassium permanganate oxidation in the mixing solutions of pyridine and water.
The synthetic method of metal-organic framework materials of the present invention, comprises the following steps:
Under air-proof condition, organic ligand H
4bCPIA (4-(3,5-bis-carboxyphenyl)-2,6-is to dicarboxyl phenylpyridine) and cupric nitrate (Cu (NO
3)
3) at DMF (DMF) and Tetrafluoroboric acid (HBF
4) mixing solutions in, obtain the crystal of this metal-organic framework via solvent thermal reaction.
Wherein organic ligand H
4bCPIA (4-(3,5-bis-carboxyphenyl)-2,6-to dicarboxyl phenylpyridine) be 1:(1 ~ 3 with the mol ratio of cupric nitrate), the N of the corresponding 1.0mL ~ 4.0mL of cupric nitrate of every 0.05 mmole, dinethylformamide, the HBF of 1 ~ 10
4, the wherein HBF of 1mL
4be about 40, the temperature of described thermal response is 60 DEG C-120 DEG C, and the reaction times is 12-48 hour.
Hole containing caged in this metal-organic framework, its hole dimension is approximately
Come from the water described in the oxygen coordination of water molecules the water comprised in solvent for use in metal-organic framework of the present invention.
Organic ligand synthesized by the present invention belongs to the low symmetrical Carboxylic acid ligand of novel four tooth.Metal-organic framework novel structure synthesized by the present invention, has potential application in gas adsorption and storage.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of the low symmetrical Carboxylic acid ligand of four teeth of this metal-organic framework of synthesis.
Fig. 2 is the secondary construction unit figure of this metal-organic framework.
Fig. 3 is the part connection mode figure of this metal-organic framework.
Fig. 4 is the structural representation in the caged hole of this metal-organic framework.
Fig. 5 is the three-dimensional plot of this metal-organic framework.
Fig. 6 is the topological diagram of this metal-organic framework.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
3,5-dimethylbenzaldehyde (2.0g, 15mmol), 4-methyl acetophenone (4.6g, 34mmol), NaOH (9.6g, 240mmol) mixed grinding, until grind to form yellow powder.This yellow powder is placed in 500mL there-necked flask, adds 300mL ethanol and 15g ammonium acetate, add thermic backflow, be incubated 24 hours.After question response terminates, be cooled to room temperature, adularescent solid is separated out, and is filtered out, and washing refilters to obtain white solid (3.4g, productive rate is 63.0%).
4-(3,5-xylyl)-2,6-xylyl pyridine (3.0g), 40mL pyridine 120mL water joins in 300mL there-necked flask, adds 4g potassium permanganate solid wherein, is heated to backflow 48 hours.To be cooledly to filter to room temperature.Filtrate adds HCl and is neutralized to pH=2, has a large amount of yellow solid to separate out, out washed by its suction filtration, dries and to obtain yellow solid (2.3g, 83.3%)
Embodiment 2
3,5-dimethylbenzaldehyde (4.0g, 30mmol), 4-methyl acetophenone (9.5g, 68mmol), NaOH (15g, 375mmol) mixed grinding, until grind to form yellow powder.This yellow powder is placed in 1000mL there-necked flask, adds 500mL ethanol and 20g ammonium acetate, add thermic backflow, be incubated 30 hours.After question response terminates, be cooled to room temperature, adularescent solid is separated out, and is filtered out, and washing refilters to obtain white solid (8.0g, productive rate is 63.0%).
4-(3,5-xylyl)-2,6-xylyl pyridine (5.0g), 50mL pyridine 150mL water joins in 300mL there-necked flask, adds 5g potassium permanganate solid wherein, is heated to backflow 48 hours.To be cooledly to filter to room temperature.Filtrate adds HCl and is neutralized to pH=2, has a large amount of yellow solid to separate out, out washed by its suction filtration, dries and to obtain yellow solid (4.2g, 83.3%)
Embodiment 3
By organic ligand H
4bCPIA (0.035 mmole) mixes in the DMF of 1mL with cupric nitrate (0.14 mmole), adds 1dHBF
4, enclose in bottle.Within 48 hours, obtain the crystal of this metal-organic framework via thermal response at 80 DEG C.
Embodiment 4
By organic ligand H
4bCPIA (0.035 mmole) mixes in the DMF of 1.5mL with cupric nitrate (0.14 mmole), adds 2dHBF
4, enclose in bottle.Within 48 hours, obtain the crystal of this metal-organic framework via thermal response at 80 DEG C.
Embodiment 5
By organic ligand H
4bCPIA (0.035 mmole) mixes in the DMF of 2.0mL with zirconium chloride (0.14 mmole), adds 3dHBF
4, enclose in bottle.Within 48 hours, obtain the crystal of this metal-organic framework via thermal response at 80 DEG C.
The test result of the product of above-described embodiment gained is identical, specifically sees following:
(1) crystal structure determination:
Choose sizeable monocrystalline under the microscope, under 100K, utilize Bruker-AXSAPEX-IICCDX-ray single crystal diffraction instrument to collect data.Data gathering uses the Mo-K α through graphite monochromator monochromatization
target ray.Raw data is collected by APEX2 software, and the absorption correction of data uses SADABS software to complete.Crystalline structure is used SHELXTL-97 program to be resolved by direct method and obtains.First determine whole non-hydrogen atom coordinate by difference functions method and method of least squares, and obtain hydrogen atom position with theoretical hydrogenation method, then with SHELXTL-97, refine is carried out to crystalline structure.Fig. 2 to Fig. 6 is shown in by structure iron.Crystallographic data is in table 1.
The crystallographic data of table 1 metal-organic framework
The four tooth Carboxylic acid ligand synthetic route charts of Fig. 1 show: the synthesis of this part is mainly through two-step reaction: be first 3,5-dimethylbenzaldehyde is deposited at NaOH, ethanol and ammonium acetate and is reacted cyclization with 4-methyl acetophenone in case, obtain 4-(3,5-xylyl)-2,6-p-Xylol yl pyridines.Secondly product previous step obtained obtains this asymmetric four tooth Carboxylic acid ligands through potassium permanganate oxidation under the mixing solutions of pyridine and water exists.
The structure iron of Fig. 2 shows: Cu in this metal-organic framework
2+ion adopt rectangular pyramid coordination mode and from the carbonyl atom O on four different ligands and an O Atomic coordinate from water.Such two Cu
2+ion and two constitute [Cu from the O atom of water and the carboxyl of four different ligands
2(H
2o)
2(COO)
4] SBU.
The structure iron of Fig. 3 shows: in this metal-organic framework, and each asymmetric four tooth Carboxylic acid ligands adopt cis-along (syn-syn) bridging coordination mode and eight Cu
2+ion coordination.
The structure iron of Fig. 4 shows: the hole that there is caged in this metal-organic framework.12 SUBs and six BCPIA
4-coordination defines octahedral cage, and its diameter is
The structure iron of Fig. 5 shows: in this metal-organic framework, each octahedral cage is connected with eight octahedra cages of surrounding with trapezoidal face by sharing trilateral, constitutes three-dimensional framework material.
The structure iron of Fig. 6 shows: if the SBUs of the double-core Cu in this metal-organic framework and four tooth Asymmetry coordinations are simplified to four connected nodes, and so this metal-organic framework can be simplified to one four net connected, and its Shi Laifuli symbol is (6
48
2), belong to the topology of Nbo type.
Claims (10)
1., based on a metal-organic framework materials of low symmetrical four tooth Carboxylic acid ligand Cu, it is characterized in that, chemical molecular formula is [Cu
2(H
2o)
2(BCPIA)], H
4bCPIA is that organic ligand 4-(3,5-bis-carboxyphenyl)-2,6-is to dicarboxyl phenylpyridine;
Organic ligand 4-(3,5-bis-carboxyphenyl)-2,6-is to dicarboxyl phenylpyridine (H
4bCPIA) chemical structural formula is:
2. according to a kind of metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu of claim 1, it is characterized in that, connect from the angle of skeleton and construct, the crystalline structure of this metal-organic framework belongs to trigonal system, spacer is R3m, and unit cell parameters is:
α=β=90 °, γ=120 °.
3., according to a kind of metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu of claim 1, it is characterized in that, each Cu in this metal-organic framework
2+ion with the coordination mode of quadrangular pyramid and an O atom from water molecules and four from the coordination of different ligands carbonyl atom O; Two Cu
2+ion is connected with the carboxyl on two O atoms from water molecules and four different ligands and constitutes classical double-core Cu and take turns that slurry type is secondary constructs cell S BU [Cu
2(H
2o)
2(COO)
4]; Each part is with cis-suitable (syn-syn) bridging coordination mode and eight Cu
2+ion coordination.
4., according to a kind of metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu of claim 3, it is characterized in that in this metal-organic framework, there is the structure of caged; 12 SUBs and six BCPIA
4-part defines an octahedra cage, and each octahedral cage is connected with eight octahedra cages of surrounding by sharing leg-of-mutton, constitutes three-dimensional framework material.
5., according to a kind of metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu of claim 4, it is characterized in that, octahedra cage inscribed sphere diameter about
6. according to a kind of metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu of claim 3, it is characterized in that, if the SBU of the double-core Cu in this metal-organic framework and four tooth Asymmetry coordinations to be simplified to the node of four connections, so this metal-organic framework is simplified to one four net connected, its Shi Laifuli symbol
for (6
48
2), belong to the topology of Nbo type.
7. prepare the method for the metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu of any one described in claim 1-6, it is characterized in that, under air-proof condition, organic ligand H
4bCPIA (4-(3,5-bis-carboxyphenyl)-2,6-is to dicarboxyl phenylpyridine) and cupric nitrate (Cu (NO
3)
3) at DMF and Tetrafluoroboric acid (HBF
4) mixing solutions in, obtain the crystal of this metal-organic framework via solvent thermal reaction.
8. according to the method for claim 7, it is characterized in that, organic ligand H
4bCPIA (4-(3,5-bis-carboxyphenyl)-2,6-is to dicarboxyl phenylpyridine) be 1:(1 ~ 3 with the mol ratio of cupric nitrate), the cupric nitrate corresponding DMF of 1.0mL ~ 4.0mL, the HBF of 1 ~ 10 of every 0.05 mmole
4, the wherein HBF of 1mL
4be about 40.
9. according to the method for claim 7, it is characterized in that, the temperature of thermal response is 60 DEG C-120 DEG C, and the reaction times is 12-48 hour.
10. organic ligand H
4bCPIA (4-(3,5-bis-carboxyphenyl)-2,6-is to dicarboxyl phenylpyridine) preparation method: be first 3,5-dimethylbenzaldehyde is deposited at NaOH, ethanol and ammonium acetate and is reacted cyclization with 4-methyl acetophenone in case, obtain 4-(3,5-xylyl)-2,6-p-Xylol yl pyridines; Secondly product previous step obtained obtains this low symmetrical four tooth Carboxylic acid ligands through potassium permanganate oxidation in the mixing solutions of pyridine and water.
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| CN107376851A (en) * | 2017-08-23 | 2017-11-24 | 三峡大学 | A kind of preparation method and applications of partial vulcanization metal organic frame composite |
| CN108586761A (en) * | 2018-04-11 | 2018-09-28 | 北京工业大学 | A kind of 3-dimensional metal-organic framework material of zirconium, preparation method and water vapor adsorption application |
| CN108586761B (en) * | 2018-04-11 | 2020-08-28 | 北京工业大学 | Three-dimensional metal-organic framework material of zirconium, preparation method and water vapor adsorption application |
| CN109336809A (en) * | 2018-11-15 | 2019-02-15 | 安徽师范大学 | The stable metal-organic framework material and its preparation method and application of performance |
| CN109456756A (en) * | 2018-12-14 | 2019-03-12 | 北京工业大学 | A kind of metal-organic framework materials of Zr, preparation method and applications |
| CN109456756B (en) * | 2018-12-14 | 2021-07-02 | 北京工业大学 | Zr metal-organic framework material, preparation method and application thereof |
| CN110982087A (en) * | 2019-12-18 | 2020-04-10 | 中国农业科学院农业质量标准与检测技术研究所 | Metal-organic framework material and preparation method and application thereof |
| CN110982087B (en) * | 2019-12-18 | 2022-05-24 | 中国农业科学院农业质量标准与检测技术研究所 | Metal-organic framework material and preparation method and application thereof |
| CN113045765A (en) * | 2021-03-23 | 2021-06-29 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method of zirconium-based metal organic framework material |
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