CN110144047A - A kind of metal-organic framework material and preparation method thereof based on D3h symmetry building block molecule - Google Patents
A kind of metal-organic framework material and preparation method thereof based on D3h symmetry building block molecule Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract 2
- 239000003446 ligand Substances 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 230000032798 delamination Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 239000013110 organic ligand Substances 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 239000010439 graphite Substances 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000013384 organic framework Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 238000005761 Biginelli synthesis reaction Methods 0.000 description 1
- -1 Calixarene compound Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical class [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000982 solution X-ray diffraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/20—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D239/22—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to ring carbon atoms
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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Abstract
This application involves one kind to be based on D3The metal-organic framework and preparation method thereof of h symmetry building block molecule.Metal-organic framework material is that a kind of organic ligand and metal ion or cluster are self-assembly of by coordinate bond, and the hybrid inorganic-organic materials with molecule inner pore and high-specific surface area are all widely used in catalysis, energy storage and separation.But current metal-organic framework material is typically based on plane building block molecule, and present patent application develops a kind of D with stereochemical structure3H symmetry building block molecule, and a series of metal organic frame porous materials are developed using the building block molecule, this kind of material has the layer structure of similar graphite, can be applied to be catalyzed, gas separation and anion selectivity screening.The metal-organic framework material unique structure, it is low in cost, there is high application value and broad application prospect.
Description
Technical field
The present invention relates to inorganic chemistry and materials science field, more particularly to a kind of based on D3h structure caged ligand
Metal organic frame porous material and preparation method thereof.
Background technique
Metal organic frame is a kind of organic inorganic hybridization coordination polymer material quickly grown in recent years, has three-dimensional
Porous structure, generally using metal ion as tie point, organic ligand support is self-assembly of with periodical mesh skeleton
Structure constitutes space 3D and extends." Metal- has been put forward for the first time from late nineteen nineties in last century O. M. Yaghi research group
Since the concept of Organic Frameworks, MOFs " (metal organic frame) (Nature, 1995,378,703-
706.), metal-organic framework material is just got the attention, and is nearly ten years even more the hot fields as material science, is obtained
It must develop on an unprecedented scale.
Due to the modular nature and temperate condition of metal-organic framework material synthesis, by reasonably selecting molecular structure list
Member can systematically adjust its material porosity, and multiple functions site can be introduced, and have both organic material and inorganic material
The advantages of material, becomes the important research direction of multiple chemical branches.Metal organic frame is as emerging multifunctional material in gas
Storage and separation, optics, electric and magnetic material, chemical sensitisation, catalysis and biomedicine etc. have important application.With
The gradually rise of the increasing and compound MOFs material of MOFs material category, before MOFs material will have immeasurable application
Scape.But and MOFs material, in molecular ion specific recognition and separation, the application performance of be catalyzed etc. is also in urgent need to be improved.
Although metal-organic framework material is quickly grown by the exploration of many years, there is also problems limit its into
One step moves towards application.Metal-organic framework material building block molecule reported at present is mostly plane small organic molecule, is had vertical
The building block molecule of body structure lacks report at present.Calixarene compound has complicated and diversified stereochemical structure, can provide multiplicity
Stereoeffect.The present patent application is based on calixarene kind compound, constructs a kind of building block molecule with D3h configuration,
And a series of metal organic frame porous materials are developed using the building block molecule, three-dimensional cage structure determines that it is different from
The special nature and application of other MOFs, has expanded the structure type of existing organic metal framework material.Because ligand itself has
Three-dimensional structure and duct, impart its special ion, molecular specificity identification, special catalysis and gas absorption property.
Summary of the invention
The present patent application discloses a kind of preparation method of metal organic frame porous material based on D3h caged ligand.
This method is raw materials used at low cost, prepares yield height, simple process, and gained metal-organic framework material structure novel is stablized, tool
Have wide application prospects.
MOFs in the present invention is prepared based on D3h caged ligand, is obtained by D3h caged ligand and metal ion self assembly
, there is the features such as synthesis is simple, and yield is high, large specific surface area.
The MOFs prepared in the present invention is to different anions and gas with certain selectivity, it can be achieved that the sieve of different component
Point.
The MOFs prepared in the present invention has the cellular structure of macropore cavity and interpenetrating, and has apparent similar
The layer structure of graphene.
The present invention provides the preparation method of the above-mentioned metal organic frame porous material based on D3h caged ligand, according to
Following step carries out:
(1) organic supermolecular ligand and metal salt are added in suitable solvent, mixed solution is transferred in glass tube, it is close
Envelope, then first heats up, and keeps temperature certain time, then cool down.Filtering, washing, obtains metal target organic framework materials.
(2) in above-mentioned steps (1), organic supermolecular ligand is one of Fig. 1 structure:
(3) in above-mentioned steps (1), metal salt is one of transition metal chromium, manganese, iron, cobalt, nickel, copper, zinc etc. soluble-salt.
(4) in above-mentioned steps (1), the solvent is organic solvent or organic solvent and aqueous mixtures.Wherein, organic solvent
It is DMF, DMSO, ethyl alcohol etc..
(5) in above-mentioned steps (1), metal salt and organic supermolecular ligand mixed proportion are 5:1-2:1.
(6) in above-mentioned steps (1), glass tube used is 10-15 mL, and quantity of solvent is 2-5 mL.
(7) in above-mentioned steps (1), heating rate 0.1-1oC/min, holding temperature are 80-150 oC, the retention time is
48-72 hours, rate of temperature fall 1-2 oC/ min, cooling need to be cooled to room temperature, and be washed for several times with corresponding solvent.
(8) the three-dimensional caged ligand structure that the present invention uses, determines that it is different from the special nature of other MOFs and application,
Help to solve metal-organic framework material ion, molecular specificity identifies problem, expanded existing organic metal framework material
Structure type.The three-dimensional structure having by ligand itself and duct are coordinated after forming metal organic frame with metal, are retained
Original structure and duct, increase the specific surface area of duct type and material in material in this way, and improving material includes catalysis
With the performance of gas absorption etc..
(9) material prepared by the present invention can realize that anion selectivity sieves, and its special class graphene stratiform
Structure can be realized by physics delamination method and be removed, and corresponding metal organic frame nanometer sheet material is obtained, and further be expanded
The application value of material.
(10) metal target organic framework materials are obtained using one kettle way in the present invention, method therefor is simple and easy, raw material
At low cost, reaction condition is mild, and yield is higher.Resulting materials are prepared, low in cost, structure novel, specific surface area is high, and performance is steady
It is fixed.With high application value and broad application prospect.
Detailed description of the invention:
Fig. 1: molecular structure Fig. 2 of D3h caged ligand according to the present invention: metal described in embodiment 2 of the present invention has machine frame
The single crystal diffraction structure spectrogram (SXRD) of frame material.Fig. 3: the scanning of metal-organic framework material described in embodiment 2 of the present invention
Electron microscope (SEM).Fig. 4: the layer structure Electronic Speculum of the lift-off structure of metal-organic framework material described in embodiment 2 of the present invention
Figure.Fig. 5: the removing single layer electron microscope of metal-organic framework material described in embodiment 2 of the present invention.
Specific embodiment:
The present invention is further described in detail below by way of production instance, the personnel of Related Research Domain base according to the present invention
The improvement or variation that this thought is made, within the scope of the present invention.Test method described in embodiment below, such as without special theory
It is bright, it is conventional method；The instrument and material commercially obtain unless otherwise specified.
Embodiment 1；The preparation (R=COOH) of Carboxylic acid ligand L1
0.05 mol Cyanuric Chloride and 0.065 mol aluminum trichloride (anhydrous) are added in 250 mL round-bottomed flasks, 100 mL are added
Toluene stirs 5-10 hours, and ice water is quenched, and organic phase is recrystallized to give intermediate product a；It will be between 3.6 g intermediate product a, 1.5 g
Benzenetriol and 5.0 g cesium carbonates react at room temperature 3-5 hours, extraction, column chromatography for separation obtains in the case where dimethyl sulfoxide is solvent condition
To intermediate product b；By 0.5 g intermediate product b, 100 mL round-bottomed flasks are added in 120 mg chromium trioxides and 320 mg periodic acid
In, 40 mL acetonitriles are added as solvent, are stirred at room temperature 8-10 hours, extract, evaporates solvent, it is as corresponding to obtain white solid
Carboxylic acid ligand L1.
Embodiment 2；A kind of preparation for the metal-organic framework material being coordinated based on Carboxylic acid ligand and copper ion
Carboxylic acid ligand 0.01-0.03mmol obtained in embodiment 1, six nitric hydrate copper 0.03-0.09mmol are added to
In 2-5mLDMSO or DMF solution, mixed solution is added in 15mL glass tube and seals, with 0.1oThe rate of C/min is warming up to 100-
140 oC, kept for 48-72 hours, then with 1oThe rate of C/min is cooled to room temperature, filtering, solvent washing, is obtained blue blocky brilliant
Body is prepared copper metal organic framework materials.
Embodiment 3；The activation of metal-organic framework material
It is first impregnated 24 hours with DMSO, is repeated twice, is impregnated 24 hours in again with methanol, in triplicate, be swapped out solvent,
80-200 oCDrying is to get the copper metal organic framework materials for arriving activation.
Embodiment 4；A kind of preparation of the metal-organic framework material based on Carboxylic acid ligand and zinc ion coordination
Implementation method only changes six nitric hydrate copper into zinc nitrate hexahydrate, obtaining white crystal is base with embodiment 2
In the zinc metal-organic framework material of Carboxylic acid ligand.
Embodiment 5；A kind of preparation for the metal-organic framework material being coordinated based on Carboxylic acid ligand and cobalt ions
Implementation method only changes six nitric hydrate copper into cabaltous nitrate hexahydrate, obtaining red crystals is base with embodiment 2
In the cobalt metal-organic framework material of Carboxylic acid ligand.
Embodiment 6；A kind of preparation of yl pyridines ligand and the 3-dimensional metal organic framework materials of copper ion coordination
Implementation method only changes Carboxylic acid ligand into pyridyl ligands with embodiment 2 to get the copper metal based on pyridine ligand
Organic framework materials.
Embodiment 7；It is sieved based on selectivity of the copper metal organic frame to anion
By the 2 non-activated copper metal organic framework materials of gained of embodiment, 0.2 g is added in 50 mL round-bottomed flasks, is added 20
ML dimethyl sulfoxide adds 0.1 M copper sulphate and each 1 mL of copper chloride, 50oC is exchanged 24 hours, and filtering detects in filtrate
Ion, only sulfate ion are exchanged, and concentration significantly reduces, and chlorine ion concentration is constant.
Embodiment 8；Delamination based on copper metal organic framework materials
By 2 metal-organic framework material of the gained without overactivation of embodiment, filtering is washed with solvent, is impregnated in DMSO
It 24 hours, is repeated twice, in DMSO solution, with 20-40% power ultra sonic bath 2-5 minutes, stands 5 minutes after ultra sonic bath,
Unstripped bulk crystals are waited to deposit, upper layer is to contain the suspension for separating nanometer laminated structure.
Embodiment 9；Shape selective catalysis based on copper metal organic framework materials
3 copper metal organic framework materials of the gained through overactivation of embodiment are taken to be added in Biginelli reaction as catalyst,
Catalyst is not added in reaction 8 hours, blank group, and reactionless generation is added in the reaction of catalytic amount copper metal organic framework materials, and R=
CH3React when smaller group and smoothly occur, R be p-nitrophenyl etc. compared with macoradical when there is no product generation.
Claims (7)
1. one kind is based on D3The metal-organic framework and preparation method thereof of h symmetry building block molecule, be primarily characterized in that by
Implement according to following steps: with D3H symmetry ligand L and metal salt are raw material, are obtained by solvent thermal reaction with class graphene
The metal-organic framework material of structure.
2. preparation method as described in claim 1, which is characterized in that D3H symmetry ligand is one of Fig. 1 structure.
3. as described in claim 1, metal salt is one of transition metal chromium, manganese, iron, cobalt, nickel, copper, zinc etc. soluble-salt.
4. as described in claim 1, solvent is organic solvent or organic solvent and aqueous mixtures.Wherein, organic solvent be DMF,
DMSO, ethyl alcohol etc..
5. as described in claim 1, material is prepared in closed container, metal salt and D3H symmetry ligand mixed proportion is 10:
1-1:1。
6. as described in claim 1, wherein heating reaction heating rate is 0.1-5oC/min, it is 60-180 that reaction, which keeps temperature,oC, temperature hold-time 24 hours or more, rate of temperature fall 0.1-10oC/min is washed for several times with corresponding solvent.
7. one kind is based on D3The metal-organic framework material of h symmetry building block molecule, which is characterized in that such metal organic frame
Lamellar structure with similar graphene, can be by either physically or chemically carrying out delamination, and lamellar spacing is empty in 1-5nm, layer
Chamber size is in 1.5-5nm；The metal organic frame can be applied to the screening of anion, gas and other chemical substances.
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| CN111718492A (en) * | 2019-11-13 | 2020-09-29 | 中南大学 | Preparation and application of large-size single-layer two-dimensional MOF nanosheet |
| CN112280053A (en) * | 2020-09-30 | 2021-01-29 | 中南大学 | Two-dimensional COFs nanosheet based on cage-shaped molecular building block and application thereof |
| CN115073494A (en) * | 2021-03-12 | 2022-09-20 | 中国科学院化学研究所 | Triazine cage-shaped compound and preparation method and application thereof |
| RU2782932C1 (en) * | 2021-11-30 | 2022-11-07 | Публичное акционерное общество "Газпром" | Block composite material for gas accumulation and method for production thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718492A (en) * | 2019-11-13 | 2020-09-29 | 中南大学 | Preparation and application of large-size single-layer two-dimensional MOF nanosheet |
| CN112280053A (en) * | 2020-09-30 | 2021-01-29 | 中南大学 | Two-dimensional COFs nanosheet based on cage-shaped molecular building block and application thereof |
| CN112280053B (en) * | 2020-09-30 | 2022-02-18 | 中南大学 | Two-dimensional COFs nanosheet based on cage-shaped molecular building block and application thereof |
| CN115073494A (en) * | 2021-03-12 | 2022-09-20 | 中国科学院化学研究所 | Triazine cage-shaped compound and preparation method and application thereof |
| CN115073494B (en) * | 2021-03-12 | 2023-06-20 | 中国科学院化学研究所 | Triazine cage compound and preparation method and application thereof |
| RU2782932C1 (en) * | 2021-11-30 | 2022-11-07 | Публичное акционерное общество "Газпром" | Block composite material for gas accumulation and method for production thereof |
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