CN110283328A - A kind of zirconium metal-organic framework material and preparation method thereof as crystal sponge - Google Patents
A kind of zirconium metal-organic framework material and preparation method thereof as crystal sponge Download PDFInfo
- Publication number
- CN110283328A CN110283328A CN201910452026.2A CN201910452026A CN110283328A CN 110283328 A CN110283328 A CN 110283328A CN 201910452026 A CN201910452026 A CN 201910452026A CN 110283328 A CN110283328 A CN 110283328A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- framework material
- preparation
- metal
- terphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 70
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 65
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 45
- 239000013078 crystal Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 16
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- KZOBYUKSQYFWQH-UHFFFAOYSA-N 4-amino-3,5-diphenylbenzonitrile Chemical compound NC1=C(C=2C=CC=CC=2)C=C(C#N)C=C1C1=CC=CC=C1 KZOBYUKSQYFWQH-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- WLZCMGXAEXFAQA-UHFFFAOYSA-N 2-amino-3,5-dibromobenzonitrile Chemical compound NC1=C(Br)C=C(Br)C=C1C#N WLZCMGXAEXFAQA-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 7
- 235000011009 potassium phosphates Nutrition 0.000 claims description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 235000002639 sodium chloride Nutrition 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000002274 desiccant Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 2
- VBDQMGVTDJKTFN-UHFFFAOYSA-N C1(=CC=CC=C1)OB(O)O.C(=O)OC Chemical compound C1(=CC=CC=C1)OB(O)O.C(=O)OC VBDQMGVTDJKTFN-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011630 iodine Substances 0.000 abstract description 7
- 229910052740 iodine Inorganic materials 0.000 abstract description 7
- 238000002441 X-ray diffraction Methods 0.000 abstract description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 7
- 229940006461 iodide ion Drugs 0.000 description 7
- 210000003850 cellular structure Anatomy 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- GLWKJSMSPGFSSM-UHFFFAOYSA-N NC1=C(C=C(C=C1C1=CC=C(C=C1)C(=O)O)C#N)C1=CC=C(C=C1)C(=O)O Chemical class NC1=C(C=C(C=C1C1=CC=C(C=C1)C(=O)O)C#N)C1=CC=C(C=C1)C(=O)O GLWKJSMSPGFSSM-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- -1 dichloromethane Alkane Chemical class 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- 229910017488 Cu K Inorganic materials 0.000 description 2
- 229910017541 Cu-K Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000159 protein binding assay Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VQEUYQIWDABATG-UHFFFAOYSA-N 3,5-diphenylbenzonitrile Chemical compound C=1C(C#N)=CC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 VQEUYQIWDABATG-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
Classifications
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
- G01N23/2005—Preparation of powder samples therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/05—Investigating materials by wave or particle radiation by diffraction, scatter or reflection
- G01N2223/056—Investigating materials by wave or particle radiation by diffraction, scatter or reflection diffraction
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/10—Different kinds of radiation or particles
- G01N2223/101—Different kinds of radiation or particles electromagnetic radiation
- G01N2223/1016—X-ray
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/60—Specific applications or type of materials
- G01N2223/604—Specific applications or type of materials monocrystal
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The zirconium metal-organic framework material and preparation method thereof that the invention discloses a kind of as crystal sponge, belongs to metal-organic framework material field.The chemical formula of the zirconium metal-organic framework material are as follows: [Zr6(μ3‑O)4(μ3‑OH)4(OH)2(H2O)2(HCOO)2(L)4]n, wherein L be 2'- amino -5'- cyano-[1,1':3'; 1 " terphenyl] -4,4 "-dioctyl phthalate, n ∞, integral frame structure is that quadruple interts metal organic framework; the zirconium metal-organic framework material category trigonal system, space group R-3c, cell parameter areα=β=90 °, γ=120 °, unit cell volume areZirconium metal-organic framework material provided in an embodiment of the present invention can realize the absorption to iodine molecule as crystal sponge, and pass through the structure of iodine after the absorption of Advances in crystal X-ray diffraction characterized by techniques.The invention has widened the application range in terms of characterizing guest molecule of metal-organic framework material, in particular for the inorganic substances for being dissolved in non-pure organic solvent.
Description
Technical field
The present invention relates to metal-organic framework material field, in particular to a kind of zirconium metal as crystal sponge has machine frame
Frame material and preparation method thereof.
Background technique
Metal-organic framework material (MOFs) one of as current popular research material, by its specific frame structure and
Hole bottom cavity blast, so that metal-organic framework material has unique application prospect in multiple fields.Metal organic frame has height
Orderly steric configuration, stable cellular structure, excellent absorption property, the component arrangement being repeated cyclically are spent, and can be utilized
Single crystal diffraction technology sufficiently spies upon its architectural difference on atomic level.Existing research starts to probe into using MOFs as carrier
The correlative study of guest molecule is tested, this strategy is referred to as crystal sponge.The advantage of the technology is can be directed to minimal amount of visitor
Body molecule clearly characterizes relative configuration and other structural informations.This is the advantage that other structures characterization method is unattainable,
Great development is thus obtained.But the technology still has its limitation, for example the guest molecule loaded focuses mostly in organic molecule,
And dicyandiamide solution can only select organic solvent, such as hexamethylene.Certainly also there are a small number of reports for inorganic substances, for example utilize monocrystalline
The structural information after single metal atom is modified after characterized by techniques MOFs.But it is directed to the crystal sponge of inorganic target molecule, especially
It is the example or very rare that can implement in non-aqueous system.Main cause is that MOFs parent is non-under pure organic environment
Rear modification in easily lose its crystallinity, and then be unsuitable for carry out monocrystalline test.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of zirconium metal-organic framework material as crystal sponge and
Preparation method, the material can be carried out as the crystal sponge for inorganic substances using so that having widened metal has machine frame
The application range of frame material.
The present invention constructs the metal-organic framework material of high stability, is prepared for by reasonable chemical regulation means
The zirconium metal-organic framework material that there is the first quadruple to intert structure.Material water stabilizing with higher, cellular structure
And higher X-ray diffraction quality.Be highly suitable as the crystal sponge for inorganic substances carry out using.The series achievement
Crystal engineering is not only illustrated for the feasibility of regulation Zr-MOF material, also illustrates and rationally constructs with particular configuration
Decisive action of the MOF for developing MOF application.
Technical solution provided by the invention is as follows:
A kind of zirconium metal-organic framework material as crystal sponge, chemical formula are as follows: [Zr6(μ3-O)4(μ3-OH)4
(OH)2(H2O)2(HCOO)2(L)4]n, wherein L is 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 "-diformazans
Acid, n ∞；
Frame structure is that quadruple interts metal organic framework, belongs to trigonal system, space group R-3c, and cell parameter isα=β=90 °, γ=120 °, unit cell volume are
The structure of the zirconium metal-organic framework material are as follows:
Another object of the present invention is to provide the preparation methods of above-mentioned zirconium metal-organic framework material, and preparation method is such as
Under, comprising the following steps:
(1) by 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 "-dioctyl phthalate is dissolved in N, N '-dimethyl
Formamide prepares mixed solution；
(2) zirconium chloride metal salt is added in above-mentioned mixed solution, formic acid is then added, is placed in 115-125 DEG C of baking
Case obtains clear crystal after standing to fully reacting, and isolating the crystal is the zirconium metal-organic framework material.
"-dioctyl phthalate exists for [1,1':3', 1 "-terphenyl] -4,4 specifically, 2'- amino -5'- cyano-in above-mentioned steps (1)
N, the concentration in N '-dimethyl formamide are 4mg/mL~6mg/mL.
Specifically, the dosage of zirconium chloride is 10-15mg in above-mentioned steps (2) in terms of 2.5~3.5mL mixed solution I；
The dosage of the formic acid is 130-170 μ L.
Specifically, 2'- amino -5'- cyano-in above-mentioned steps (1) [1,1':3', 1 "-terphenyl] -4,4 "-dioctyl phthalate
The preparation method is as follows:
(1) under nitrogen atmosphere, 3,5- dibromo aminobenzonitrile, 4- phenyl boric acid methyl formate and potassium phosphate are added to Isosorbide-5-Nitrae-
It is dissolved in dioxane, tetrakis triphenylphosphine palladium is then added, be back to complete reaction, be cooled to room temperature；
(2) after evaporating organic solvent, methylene chloride and water is added, organic phase is separated, then by water phase dichloromethane
Alkane extracts three times, merges organic phase and is extracted with saturated common salt water washing, and is removed water to obtain solution A with desiccant；
(3) by solution A evaporating organic solvent, then solid is dry, obtain 2'- amino -5'- cyano-[1,1':3',
1'- terphenyl] -4,4 "-dicarboxylic esters；
(4) by 2'- amino -5'- cyano-[1,1':3', 1'- terphenyl] -4,4, "-dicarboxylic ester, which is dissolved in methanol, to be obtained
Solution is added NaOH, gained mixture is being stirred overnight, then methanol removed by evaporation, a large amount of water are added later, will be aqueous
Residue is acidified to pH=2~3 with hydrochloric acid, filters gained sediment and is washed with distilled water；
(5) sediment is vacuum dried, obtain 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 "-two
Formic acid.
Specifically, 3,5- dibromo aminobenzonitrile, 4- phenyl boric acid methyl formate, potassium phosphate and four (triphens in above-mentioned steps (1)
Base phosphine) palladium molar ratio be 16.0-16.8mmol:38.0-40.0mmol:93.0-95.0mmol:1.1-1.3mmol.
Specifically, reflux temperature is 80-100 DEG C in above-mentioned steps (1), return time is 45-50 hours.
Specifically, the volume ratio of methylene chloride and water is 2:1 in above-mentioned steps (2).
Specifically, -4,4 "-dicarboxylic acids of 2'- amino -5'- cyano-[1,1':3', 1'- terphenyl] in above-mentioned steps (4)
The amount ratio of ester, methanol and NaOH is 10.0-12.0mmol:100mL:37.0-38.5mmol.
Specifically, drying temperature is 80 DEG C in above-mentioned steps (3), (5).
2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 "-dioctyl phthalate synthetic route is as follows:
Beneficial effects of the present invention:
(1) zirconium metal organic frame material provided by the invention has stable Zr6Cluster unit, strong Zr-O phase interaction
With stable cellular structure, especially its quadruple, which intert structure, can guarantee that the material has tightly packed mode, improve crystalline substance
Performance of the state material in the derivative test of X-ray, overcomes it as crystal sponge in the technical defect of single crystal diffraction；
(2) the crystal sponge prepared by is the material that can be used in adsorbing the polymeric species of elemental iodine；
(3) the zirconium metal-organic framework material can not only effectively solve metal-organic framework material to new opplication field
Demand, additionally it is possible to which the application range of metal-organic framework material has been widened in the performance for effectively promoting material crystals test aspect；
(4) preparation method is simple, and can prepare the higher zirconium metal-organic framework material of purity；
(5) preparation for the crystal sponge for inorganic substances provides a kind of new approaches, has opened up particular configuration MOF's
Using.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of zirconium metal-organic framework material provided in an embodiment of the present invention；
Fig. 2 is the X-ray single crystal diffraction spectrogram of zirconium metal-organic framework material provided in an embodiment of the present invention；
Fig. 3 is the ray powder X-ray diffraction spectrogram of zirconium metal-organic framework material provided in an embodiment of the present invention；
Fig. 4 is the accumulation graph after the absorption iodine of zirconium metal-organic framework material provided in an embodiment of the present invention；
Fig. 5 is the monocrystalline X of the single crystal samples of iodine after zirconium metal-organic framework material provided in an embodiment of the present invention absorption iodine
X ray diffration pattern x.
Specific embodiment
The present invention is further described combined with specific embodiments below, and the contents of the present invention are completely without being limited thereto.
The embodiment of the invention provides a kind of zirconium metal-organic framework material as crystal sponge, the zirconium metal is organic
The chemical formula of frame material are as follows: [Zr6(μ3-O)4(μ3-OH)4(OH)2(H2O)2(HCOO)2(L)4]n, wherein L is 2'- amino-
"-dioctyl phthalate, n ∞, it is organic that integral frame structure is that quadruple interts metal to 5'- cyano-[1,1':3', 1 "-terphenyl] -4,4
Skeleton, the zirconium metal-organic framework material category trigonal system, space group R-3c, cell parameter are α=β=90 °, γ=120 °, unit cell volume areThe structure of the zirconium metal-organic framework material are as follows:
Embodiment 1
Prepare zirconium metal organic frame
The preparation method is as follows:
1,2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 is prepared "-dioctyl phthalate:
(1) under nitrogen atmosphere, 3,5- dibromo aminobenzonitrile (16.0mmol), 4- phenyl boric acid methyl formate
(38.0mmol), potassium phosphate (93.0mmol) are added in Isosorbide-5-Nitrae-dioxane (500mL) solvent, and four (triphenylphosphines) are added
Temperature is risen to 80 DEG C later by palladium (1.1mmol), is flowed back 45 hours, is cooled to room temperature；
(2) after removing organic solvent by rotary evaporation, methylene chloride (100mL) and H is added2O (50mL) is separated organic
Then water phase is extracted three times with methylene chloride (60mL), merges organic phase and extracted with saturated common salt water washing, and with anhydrous by phase
MgSO4It is dried to obtain solution A；
(3) solution A is rotated into evaporating organic solvent, solid is dried at 80 DEG C, obtains 2'- amino -5'-
Cyano-[1,1':3', 1'- terphenyl] -4,4 "-dicarboxylic ester 4.2g, yield 66.7%；
(4) to 2'- amino -5'- cyano-[1,1':3', 1'- terphenyl] -4,4 "-dicarboxylic ester (10.0mmol)
NaOH (37.0mmol) is added in MeOH (100mL) solution, gained mixture is stirred overnight at 80 DEG C, then rotation is steamed
Hair removes MeOH, and a large amount of water are added later, aqueous residue is acidified to pH=2~3 with 2M HCl, filtering gained sediment is simultaneously
It is washed with distilled water；
(5) sediment is dried in vacuo at 80 DEG C, obtains 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -
4,4 "-dicarboxylic acids 3.5g, yield 89.7%.
2, zirconium metal organic frame is prepared
(1) 14mg 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 is weighed "-dioctyl phthalate is dissolved in
2.5mL N, preparation mixed solution I is placed in reaction flask in N '-dimethyl formamide；
(2) zirconium chloride metal salt 10mg is directly added into mixed solution I, after being rapidly added 130 μ L of formic acid, is placed in
115 DEG C of baking oven obtains clear crystal after standing after placing five days, and isolating the crystal is the zirconium metal organic frame
Material.Crystalline material and reaction solution are separated using the method for centrifugation, the revolving speed of centrifugation is 3000r/min, and the time of centrifugation is
5min。
Embodiment 2
Prepare zirconium metal organic frame
The preparation method is as follows:
1,2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 is prepared "-dioctyl phthalate:
(1) under nitrogen atmosphere, 3,5- dibromo aminobenzonitrile (16.8mmol), 4- phenyl boric acid methyl formate
(40.0mmol), potassium phosphate (95.0mmol) are added in Isosorbide-5-Nitrae-dioxane (550mL) solvent, and four (triphenylphosphines) are added
Temperature is risen to 100 DEG C later by palladium (1.3mmol), is flowed back 50 hours, is cooled to room temperature；
(2) after removing organic solvent by rotary evaporation, methylene chloride (100mL) and H is added2O (50mL) is separated organic
Then water phase is extracted three times with methylene chloride (60mL), merges organic phase and extracted with saturated common salt water washing, and with anhydrous by phase
MgSO4It is dried to obtain solution A；
(3) solution A is rotated into evaporating organic solvent, solid is dried at 80 DEG C, obtains 2'- amino -5'-
Cyano-[1,1':3', 1'- terphenyl] -4,4 "-dicarboxylic ester 4.8g, yield 65.2%；
(4) to 2'- amino -5'- cyano-[1,1':3', 1'- terphenyl] -4,4 "-dicarboxylic ester (12.0mmol)
NaOH (38.5mmol) is added in MeOH (100mL) solution, gained mixture is stirred overnight at 80 DEG C, then rotation is steamed
Hair removes MeOH, and a large amount of water are added later, aqueous residue is acidified to pH=2~3 with 2M HCl, filtering gained sediment is simultaneously
It is washed with distilled water；
(5) sediment is dried in vacuo at 80 DEG C, obtains 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -
4,4 "-dicarboxylic acids 3.9g, yield 88.9%.
2, zirconium metal organic frame is prepared
(1) 18mg 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 is weighed "-dioctyl phthalate is dissolved in
3.5mL N, preparation mixed solution I is placed in reaction flask in N '-dimethyl formamide；
(2) zirconium chloride metal salt 15mg is directly added into mixed solution I, after being rapidly added 170 μ L of formic acid, is placed in
125 DEG C of baking oven obtains clear crystal after standing after placing five days, and isolating the crystal is the zirconium metal organic frame
Material.Crystalline material and reaction solution are separated using the method for centrifugation, the revolving speed of centrifugation is 3000r/min, and the time of centrifugation is
5min。
Embodiment 3
Prepare zirconium metal organic frame
The preparation method is as follows:
1,2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 is prepared "-dioctyl phthalate:
(1) under nitrogen atmosphere, 3,5- dibromo aminobenzonitrile (16.4mmol), 4- phenyl boric acid methyl formate
(39.0mmol), potassium phosphate (94.0mmol) are added in Isosorbide-5-Nitrae-dioxane (530mL) solvent, and four (triphenylphosphines) are added
Temperature is risen to 90 DEG C later by palladium (1.2mmol), is flowed back 48 hours, is cooled to room temperature；
(2) after removing organic solvent by rotary evaporation, methylene chloride (100mL) and H is added2O (50mL) is separated organic
Then water phase is extracted three times with methylene chloride (60mL), merges organic phase and extracted with saturated common salt water washing, and with anhydrous by phase
MgSO4It is dried to obtain solution A；
(3) solution A is rotated into evaporating organic solvent, solid is dried at 80 DEG C, obtains 2'- amino -5'-
Cyano-[1,1':3', 1'- terphenyl] -4,4 "-dicarboxylic ester 4.5g, yield 66.2%；
(4) to 2'- amino -5'- cyano-[1,1':3', 1'- terphenyl] -4,4 "-dicarboxylic ester (11.0mmol)
NaOH (38.0mmol) is added in MeOH (100mL) solution, gained mixture is stirred overnight at 80 DEG C, then rotation is steamed
Hair removes MeOH, and a large amount of water are added later, aqueous residue is acidified to pH=2~3 with 2M HCl, filtering gained sediment is simultaneously
It is washed with distilled water；
(5) sediment is dried in vacuo at 80 DEG C, obtains 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -
4,4 "-dicarboxylic acids 3.7g, yield 89.5%.
2, zirconium metal organic frame is prepared
(1) 16mg 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 is weighed "-dioctyl phthalate is dissolved in
3.0mL N, preparation mixed solution I is placed in reaction flask in N '-dimethyl formamide；
(2) zirconium chloride metal salt 13mg is directly added into mixed solution I, after being rapidly added 150 μ L of formic acid, is placed in
120 DEG C of baking oven obtains clear crystal after standing after placing five days, and isolating the crystal is the zirconium metal organic frame
Material.Crystalline material and reaction solution are separated using the method for filtering.
Application Example 1
1, zirconium metal-organic framework material structured testing
1) structure determination is carried out to zirconium metal-organic framework material prepared by embodiment 1, specifically, measurement obtains the iron
The monocrystalline size of metal-organic framework material is 0.2mm × 0.1mm × 0.1mm, and Cu-K α is used on Bruker Venture Measurement, and in 100K, (empirical absorption correction of all data is all included by program to single crystal data
Software complete) measure the structure of the zirconium metal-organic framework material as shown in Figure 1, in test, structure elucidation and refine
It is to be obtained by SHELXS-2014 program, all non-hydrogen atoms use complete matrix least square method (full-
matrixleast-squares refinement based on F2) carry out structure refinement；All non-hydrogen atoms all do it is each to
Anisotropic refine；Hydrogen atom on ligand is geometrically symmetric generation and c h bond is a length ofBinding assay result is it is found that the zirconium
The chemical formula of metal-organic framework material are as follows: [Zr6(μ3-O)4(μ3-OH)4(OH)2(H2O)2(HCOO)2(L)4]n, wherein L is
"-dioctyl phthalate, n ∞, integral frame structure are interspersed for quadruple for 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4
Metal organic framework, the zirconium metal-organic framework material category trigonal system, space group R-3c, cell parameter areα=β=90 °, γ=120 °, unit cell volume areIts minimum asymmetric cell includes four zirconium ions and two ligands.Four zirconium ions pass through symmetric growth shape
At stable Zr6Clustering architecture, periphery modify eight ligands and form the network configuration with larger cellular structure.Its monocrystalline X- is penetrated
Ray diffraction diagram is as shown in Figure 2.
2) each zirconium cluster is connected by eight ligands；Each ligand connects two zirconium clusters, forms PtS configuration coordination net
Network remains biggish cellular structure.Cellular structure is occupied to form the interspersed gold of final quadruple by other triple identical grids
Belong to organic framework materials.
2, structural characterization and performance test after absorption elemental iodine
Test method:
Zirconium metal-organic framework material 5-10mg prepared by embodiment 1 is weighed, the water containing iodine 10-20mg is placed in
With acetonitrile mixed solution 3-4mL (volume ratio 1/30).
1) Morphological Characterization of the zirconium metal-organic framework material is measured, specifically, using Mercury program to list
Crystal structure is fitted to obtain powder diffraction data, and the powder diffraction spectrum actually measured with zirconium metal-organic framework material sample into
Row compares, as shown in figure 3, it can be found that going out peak position basic one after zirconium metal organic frame absorption iodide ion after comparing
It causes, it follows that the resulting zirconium metal-organic framework material purity of the present embodiment and structure are homogeneous compared with experimental fit structure
Symbol, the sample after adsorbing iodide ion equally keep higher stability.
2) structure determination is equally carried out to the single crystal samples after absorption iodide ion, specifically, measurement, which obtains the ferrous metal, to be had
The monocrystalline size of machine frame frame material is 0.2mm × 0.1mm × 0.1mm, and Cu-K α is used on Bruker VentureMeasurement, and in 100K, (empirical absorption correction of all data is all included by program to single crystal data
Software complete) measure the structure of the zirconium metal-organic framework material as shown in Figure 1, in test, structure elucidation and refine
It is to be obtained by SHELXS-2014 program, all non-hydrogen atoms use complete matrix least square method (full-
matrixleast-squares refinement based on F2) carry out structure refinement；All non-hydrogen atoms all do it is each to
Anisotropic refine；Hydrogen atom on ligand is geometrically symmetric generation and c h bond is a length ofBinding assay result is it is found that the zirconium
The chemical formula of metal-organic framework material are as follows: { [Zr6(μ3-O)4(μ3-OH)4(OH)2(H2O)2(HCOO)2(L)4]6·3(I18)·
2(I9)·4(I6) 20 (I), wherein L is 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 "-dioctyl phthalate, n
For ∞, integral frame structure is that quadruple interts metal organic framework, the zirconium metal-organic framework material category trigonal system, space
Group is R-3c, and cell parameter is α=β=90 °, γ=
120 °, unit cell volume isCellular structure after adsorbing iodide ion is identical as original skeleton structure, quilt in duct
Iodide ion occupies, as shown in Figure 4.Particular, it is important that the sample after absorption iodide ion still is able to keep higher crystallinity, accord with
Close single crystal X-ray diffraction demand.Its Advances in crystal X-ray diffraction figure is as shown in Figure 5.
3) the zirconium metal organic frame after adsorbing iodide ion presents three kinds of different structures due to the confinement effect in duct
Type.Serial achievement illustrates that the zirconium metal-organic framework material of this patent report can adsorb nothing in non-organic solvent system
Higher monocrystalline crystallinity is still kept after machine substance, meets metal-organic framework material as the crystal sea for inorganic substances
Continuous attribute specification.Therefore, this patent reports the zirconium metal-organic framework material for interting structure with quadruple for the first time, high
Stability the zirconium metal-organic framework material can be made to be applied as the crystal sponges of inorganic substances.The achievement is not
The strategy of constructing for only having expanded zirconium metal organic frame has also absolutely proved crystallography control measures for constructing with specific function
The importance of the metal-organic framework material of energy.
The foregoing is only a preferred embodiment of the present invention, but the scope of protection of the invention be not limited thereto,
Any modification that anyone skilled in the art is made in the technical scope disclosed by the present invention, equivalent replacement and
Improve etc., it should be included within the protection scope of invention.
Claims (10)
1. a kind of zirconium metal-organic framework material as crystal sponge, it is characterised in that:
The chemical formula of the zirconium metal-organic framework material are as follows: [Zr6(μ3-O)4(μ3-OH)4(OH)2(H2O)2(HCOO)2(L)4]n,
Wherein, L is 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 "-dioctyl phthalate, n ∞；
Frame structure is that quadruple interts metal organic framework, belongs to trigonal system, space group R-3c, and cell parameter isα=β=90 °, γ=120 °, unit cell volume are
The structure of the zirconium metal-organic framework material are as follows:
2. a kind of preparation method of zirconium metal-organic framework material described in claim 1, which is characterized in that including following step
It is rapid:
(1) by 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 "-dioctyl phthalate is dissolved in N, N '-dimethyl formyl
Amine prepares mixed solution I；
(2) zirconium chloride metal salt is added in above-mentioned mixed solution, formic acid is then added, is placed in 115-125 DEG C of baking oven, it is quiet
Clear crystal is obtained after setting to fully reacting, isolating the crystal is the zirconium metal-organic framework material.
3. preparation method according to claim 2, it is characterised in that: 2'- amino -5'- cyano-in the step (1) [1,
1':3', 1 "-terphenyl] -4,4 " the concentration of-dioctyl phthalate in N, N '-dimethyl formamide be 4mg/mL~6mg/mL.
4. preparation method according to claim 2, it is characterised in that: in terms of 2.5~3.5mL mixed solution I, the step
(2) dosage of zirconium chloride is 10-15mg in；The dosage of the formic acid is 130-170 μ L.
5. preparation method according to claim 2, which is characterized in that 2'- amino -5'- cyano-in the step (1) [1,
1':3', 1 "-terphenyl] -4,4 "-dioctyl phthalate the preparation method is as follows:
(1) under nitrogen atmosphere, 3,5- dibromo aminobenzonitrile, 4- phenyl boric acid methyl formate and potassium phosphate are added to Isosorbide-5-Nitrae-dioxy
It is dissolved in six rings, tetrakis triphenylphosphine palladium is then added, be back to complete reaction, be cooled to room temperature；
(2) after evaporating organic solvent, methylene chloride and water is added, separates organic phase, then extracts water phase methylene chloride
It takes three times, merges organic phase and extracted with saturated common salt water washing, and removed water to obtain solution A with desiccant；
(3) by solution A evaporating organic solvent, then solid is dry, obtain 2'- amino -5'- cyano-[1,1':3', 1'-
Terphenyl] -4,4 "-dicarboxylic ester；
(4) by 2'- amino -5'- cyano-[1,1':3', 1'- terphenyl] -4,4 "-dicarboxylic esters, which are dissolved in methanol, obtains solution,
NaOH is added, gained mixture is being stirred overnight, then methanol removed by evaporation, a large amount of water is added later, by aqueous residue
PH=2~3 are acidified to hydrochloric acid, filter gained sediment and are washed with distilled water；
(5) sediment is vacuum dried, obtain 2'- amino -5'- cyano-[1,1':3', 1 "-terphenyl] -4,4 "-diformazans
Acid.
6. preparation method according to claim 5, it is characterised in that: 3,5- dibromo aminobenzonitrile, 4- in the step (1)
The molar ratio of phenyl boric acid methyl formate, potassium phosphate and tetrakis triphenylphosphine palladium is 16.0-16.8mmol:38.0-40.0mmol:
93.0-95.0mmol:1.1-1.3mmol.
7. preparation method according to claim 5, it is characterised in that: reflux temperature is 80-100 DEG C in the step (1),
Return time is 45-50 hours.
8. preparation method according to claim 5, it is characterised in that: the volume of methylene chloride and water in the step (2)
Than for 2:1.
9. preparation method according to claim 5, it is characterised in that: 2'- amino -5'- cyano-in the step (4) [1,
1':3', 1'- terphenyl] -4, the amount ratio of 4 "-dicarboxylic esters, methanol and NaOH is 10.0-12.0mmol:100mL:37.0-
38.5mmol。
10. preparation method according to claim 5, it is characterised in that: drying temperature is 80 in the step (3), (5)
℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910452026.2A CN110283328B (en) | 2019-05-28 | 2019-05-28 | Zirconium metal organic framework material used as crystal sponge and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910452026.2A CN110283328B (en) | 2019-05-28 | 2019-05-28 | Zirconium metal organic framework material used as crystal sponge and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110283328A true CN110283328A (en) | 2019-09-27 |
| CN110283328B CN110283328B (en) | 2021-12-07 |
Family
ID=68002647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910452026.2A Expired - Fee Related CN110283328B (en) | 2019-05-28 | 2019-05-28 | Zirconium metal organic framework material used as crystal sponge and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110283328B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010899A (en) * | 2020-08-17 | 2020-12-01 | 武汉大学 | Trivalent phosphine-based molecular clamp, preparation method thereof, metal-molecular clamp catalyst, preparation method and application thereof |
| CN112934204A (en) * | 2021-02-23 | 2021-06-11 | 上海交通大学 | Heavy metal mercury adsorbent and preparation method thereof |
| CN113024824A (en) * | 2019-12-25 | 2021-06-25 | 同济大学 | Cyano-functionalized metal organic framework material and preparation method thereof |
| CN113354828A (en) * | 2021-05-08 | 2021-09-07 | 沈阳大学 | Preparation and application of novel stable metal organic framework material |
| CN114672036A (en) * | 2022-03-28 | 2022-06-28 | 北京航空航天大学 | Metal organic framework material with basic functional group and preparation method thereof |
| CN116333328A (en) * | 2023-02-23 | 2023-06-27 | 暨南大学 | Preparation method and application of novel copper-based pyridine fluorene crystal sponge |
| 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 |
| CN116554047A (en) * | 2023-07-07 | 2023-08-08 | 吉林省卓材新研科技有限公司 | Ligand, metal organic framework material, application of ligand and metal organic framework material and supercapacitor |
| EP4063839A4 (en) * | 2019-11-21 | 2023-11-22 | Kirin Holdings Kabushiki Kaisha | Preparation method of crystal structure analysis sample for structural analysis using crystal sponge method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016043122A1 (en) * | 2014-09-16 | 2016-03-24 | 国立大学法人静岡大学 | Coordination polymer compound, porous material, anion remover, and anion removal method |
| US20170016139A1 (en) * | 2016-08-31 | 2017-01-19 | Takeda Pharmaceutical Company Limited | Method for Producing Single Crystal of Polymer-Metal Complex |
| CN108912339A (en) * | 2018-06-28 | 2018-11-30 | 江汉大学 | A kind of ferrous metal organic framework materials and preparation method thereof |
-
2019
- 2019-05-28 CN CN201910452026.2A patent/CN110283328B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016043122A1 (en) * | 2014-09-16 | 2016-03-24 | 国立大学法人静岡大学 | Coordination polymer compound, porous material, anion remover, and anion removal method |
| US20170016139A1 (en) * | 2016-08-31 | 2017-01-19 | Takeda Pharmaceutical Company Limited | Method for Producing Single Crystal of Polymer-Metal Complex |
| CN108912339A (en) * | 2018-06-28 | 2018-11-30 | 江汉大学 | A kind of ferrous metal organic framework materials and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| WILLIAM J. GEE, ET AL: "Evaluating Iodine Uptake in a Crystalline Sponge Using Dynamic X‑ray Crystallography", 《INORG. CHEM.》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4063839A4 (en) * | 2019-11-21 | 2023-11-22 | Kirin Holdings Kabushiki Kaisha | Preparation method of crystal structure analysis sample for structural analysis using crystal sponge method |
| CN113024824A (en) * | 2019-12-25 | 2021-06-25 | 同济大学 | Cyano-functionalized metal organic framework material and preparation method thereof |
| CN112010899A (en) * | 2020-08-17 | 2020-12-01 | 武汉大学 | Trivalent phosphine-based molecular clamp, preparation method thereof, metal-molecular clamp catalyst, preparation method and application thereof |
| CN112010899B (en) * | 2020-08-17 | 2022-03-04 | 武汉大学 | Trivalent phosphine-based molecular clamp, preparation method thereof, metal-molecular clamp catalyst, preparation method and application thereof |
| CN112934204A (en) * | 2021-02-23 | 2021-06-11 | 上海交通大学 | Heavy metal mercury adsorbent and preparation method thereof |
| CN113354828A (en) * | 2021-05-08 | 2021-09-07 | 沈阳大学 | Preparation and application of novel stable metal organic framework material |
| CN114672036A (en) * | 2022-03-28 | 2022-06-28 | 北京航空航天大学 | Metal organic framework material with basic functional group and preparation method thereof |
| CN116333328A (en) * | 2023-02-23 | 2023-06-27 | 暨南大学 | Preparation method and application of novel copper-based pyridine fluorene crystal sponge |
| 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 |
| CN116554047A (en) * | 2023-07-07 | 2023-08-08 | 吉林省卓材新研科技有限公司 | Ligand, metal organic framework material, application of ligand and metal organic framework material and supercapacitor |
| CN116554047B (en) * | 2023-07-07 | 2023-10-20 | 吉林省卓材新研科技有限公司 | Ligand, metal organic framework material, application of ligand and metal organic framework material and supercapacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110283328B (en) | 2021-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110283328A (en) | A kind of zirconium metal-organic framework material and preparation method thereof as crystal sponge | |
| CN102276658B (en) | Mixed ligand cobalt (II) coordination compound as well as preparation method and application thereof | |
| CN106832268A (en) | Hollow spheres covalent organic frame material, preparation method, purposes and its intermediate | |
| CN110218333B (en) | Pyridine methylene phosphonic acid nickel coordination polymer and preparation method and application thereof | |
| CN112940270B (en) | MOFs material for adsorbing and separating rhenium or technetium and preparation method and application thereof | |
| CN107722287A (en) | A kind of surface hydrophobicity metal-organic framework material and its preparation and application | |
| Lu et al. | Pore space partition via secondary metal ions entrapped by pyrimidine hooks: influences on structural flexibility and carbon dioxide capture | |
| CN114621453B (en) | Preparation and application of zirconium metal organic framework material of difunctional pyridine carboxylic acid porphyrin ligand | |
| Zhao et al. | A dual-functional 3D cerium MOF heterogeneous catalyst for catalysing Knoevenagel condensation and cyanosilylation | |
| CN108424527B (en) | Synthetic method of Zn (II) complex of three-dimensional mixed ligand and application of fluorescent probe | |
| CN107413385B (en) | Microporous thulium coordination polymer as heterogeneous catalysis material and preparation method thereof | |
| CN109851559A (en) | A kind of metal-organic framework materials and preparation method and applications of the nickel based on both ends Pyrazole Ligands | |
| CN104844633A (en) | High-temperature solvothermal synthesis and application of tetranuclear Ag(I) cluster based on methylpyridine-triazole | |
| Moore et al. | Mitridatite, Ca6 (H2O) 6 [Fe93+ O6 (PO4) 9]. 3H2O. A noteworthy octahedral sheet structure | |
| CN109400902A (en) | A kind of double-core nickel coordination polymer and its preparation method and application | |
| Thompson et al. | Synthesis of [(C6H5NH) PNC6H5] 3: a participant in a phosphorus (III)-nitrogen compound trimer-dimer interconversion reaction | |
| CN104130292A (en) | Three dimensional coordination polymer with double core structure and preparation method thereof | |
| CN107987280B (en) | Aromatic cadmium sulfonate complex, preparation method and application thereof | |
| CN101406826B (en) | Coordination polymer having solvent selectivity reversible adsorption and preparation method thereof | |
| CN104130293A (en) | Three dimensional coordination polymer of mixing ligand and preparation method thereof | |
| CN114907571B (en) | Preparation and application of Eu metal-organic framework material based on difunctional pyridine carboxylic acid porphyrin ligand | |
| CN113845663B (en) | Organic uranyl phosphonate crystalline state porous fluorescent material and preparation method and application thereof | |
| CN103087084A (en) | Organometallic compound and preparation method and application thereof | |
| Braga et al. | Polymorphism, crystal transformations and gas–solid reactions | |
| CN106188109A (en) | The double triazole two dimension cadmium complex monocrystalline of 1,4 dibromo 2,5 dimethylenes and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20211207 |