CN107474060B - It is a kind of with the metal-organic framework materials and its preparation method and application for being selectively adsorbing and separating anionic dye performance - Google Patents
It is a kind of with the metal-organic framework materials and its preparation method and application for being selectively adsorbing and separating anionic dye performance Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 12
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 10
- OCIQCJGUFXWRID-UHFFFAOYSA-N 4-[3-(4-carboxyphenyl)-2h-imidazol-1-yl]benzoic acid Chemical class C1=CC(C(=O)O)=CC=C1N1C=CN(C=2C=CC(=CC=2)C(O)=O)C1 OCIQCJGUFXWRID-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012964 benzotriazole Substances 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical class [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 claims 1
- 125000005605 benzo group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000002845 discoloration Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- VOFUROIFQGPCGE-UHFFFAOYSA-N nile red Chemical compound C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=O)C2=C1 VOFUROIFQGPCGE-UHFFFAOYSA-N 0.000 description 3
- 239000013259 porous coordination polymer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- YJCYHGYOXHANSY-UHFFFAOYSA-N 4-(1h-imidazol-2-yl)benzoic acid Chemical class C1=CC(C(=O)O)=CC=C1C1=NC=CN1 YJCYHGYOXHANSY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- -1 over time Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table 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
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of with the metal-organic framework materials and its preparation method and application for being selectively adsorbing and separating anionic dye performance.Its composition is represented by the chemical formula are as follows: C60H39ClN14O10Zn4, with positively charged, (1,3- bis- (4- carboxyl phenyl) imidazoles villaumite is main ligand, 1-H benzotriazole is assistant ligand, and solvent is n,N-Dimethylformamide, benzotriazole and metal zinc ion form four core Zn clusters, then connect into hexagonal cavernous structure by diacid.The material has good chemical stability and thermal stability, has the function of selective absorption to anionic dye, and show good separating effect.Provided by the invention preparation method is simple, short preparation period and easily recycling.Ideal adsorption agent is provided for processing dye discoloration.
Description
Technical field
The present invention relates to metal-organic framework materials synthesis technical fields, and in particular to an example is based on positive charge (1,3-
Two (4- carboxyl phenyl) imidazoles villaumites are that cationic metal-organic framework materials of main ligand are used for anion as adsorbent
The quick adsorption of dyestuff with separate.
Background technique
Metal-organic framework (Metal-Organic Framework, MOFs), also known as Porous coordination polymer
(Porous CoordinationPolymers, PCPs) is to pass through coordination key-shaped by metal ion or metal cluster and organic ligand
At one kind there is the crystalline state porous framework material of periodic network structure, because of its high-specific surface area, the spies such as porous, structure is adjustable
Property, there is potential application prospect in terms of the adsorbing separation of gas, catalysis, sensing and proton.Referring to:
Nandasiri,M.I.；Jambovane,S.R.；McGrail,B.P.； Schaef,H.T.；Nune,
S.K.Coord.Chem.Rev.2016,311,38-52；H.Furukawa,N.Ko, Y.B.Go,N.Aratani,S.B.Choi,
E.Choi,A.Yazaydin,R.Q.Snurr,M.O'Keeffe, J.Kim,O.M.Yaghi,Science 2010,329,
424. are used as a polyporous materials, and MOFs has become research main-guest chemistry due to the Scalability in its duct and cage
Focus.In recent years, it is based on ion exchange and Subjective and Objective electrostatic interaction, constructs the MOFs of ionic for different charges
The report of Dye Adsorption separation is more and more, but in the ionic MOFs of these reports, the sun based on organic ligand building
The metal-organic framework materials of ionic are more rare.Referring to: Han, Y.；Sheng,S.；Yang,F.；Xie,Y. B.；Zhao,
M.J.；Li,J.R.Journal ofMaterials ChemistryA.2015,3,12804；Song,B. Q.；Wang,X.L.；
Zhang,Y.T.；Wu,X.S.；Liu,H.S.；Shao,K.Z.；Su,Z.M.；Chem. Commun.,2015,51,9515.
Summary of the invention
The performance of aspect is separated to Dye Adsorption it is an object of the invention to explore ionic type metal-organic framework materials,
A kind of metal-organic framework materials are provided, while also providing a kind of preparation method of metal-organic framework materials.The frame
Frame material is the metal-organic framework of the poroid cationic of an example supermolecule, has biggish 1-dimention nano hole in a axis direction
Road, structure have relatively high chemical stability and thermal stability, have the function of selective absorption to anionic dye,
And show good separating effect, it has broad application prospects in materials science field.
Technical solution of the present invention:
It is a kind of with the metal-organic framework materials for being selectively adsorbing and separating anionic dye performance, chemical formula is
C60H39ClN14O10Zn4, with it is positively charged (1,3- bis- (4- carboxyl phenyl) imidazoles villaumite for main ligand, 1-H benzotriazole
For assistant ligand, solvent is n,N-Dimethylformamide, and benzotriazole and metal zinc ion form four core Zn clusters, then pass through two
Acid connects into hexagonal cavernous structure, passes through strong hydrogen bonding (C-HCl) between adjacent 2D layer and is linked to be three-dimensional oversubscription
Subframe, porosity 52.8%；The metal-organic framework materials crystal belongs to monoclinic system, P21/ m space group, structure cell ginseng
Number is respectively as follows: α=γ=
90 °, β=102.18 °；The decomposition temperature for being coordinated frame is 320 DEG C.
The preparation method of the metal-organic framework materials, comprising the following steps:
1) by organic ligand (1,3- bis- (4- carboxyl phenyl) imidazoles villaumite and benzotriazole and zinc nitrate hexahydrate
It is placed in 3mL n,N-Dimethylformamide solvent, this mixed solution is put into 10ml vial, ultrasonic 30min, mixing
Uniformly；
2) sealing of above-mentioned vial is placed in 85 DEG C of baking oven, carries out incubating solvent thermal response, reacted 72 hours
Afterwards, yellow bulk crystals can be obtained；
3) up to the metal-organic framework after above-mentioned yellow crystals being washed with N,N-dimethylformamide respectively, being dry
Material.
It is further, described that (1,3- bis- (4- carboxyl phenyl) imidazoles villaumite, benzotriazole and zinc nitrate hexahydrate rub
You are than being 1:1:2.
Further, (amount ratio of 1,3- bis- (4- carboxyl phenyl) imidazoles villaumite and solvent is 0.05 mM: 3 milli
It rises.
A kind of application of the cationic metal-organic framework materials, can be used as adsorbent, for anionic dye
Quick adsorption with separate, method be by the crystalline material by ethyl alcohol carry out exchange of solvent, be then separately immersed in six kinds of differences
It is real using liquid ultraviolet detection means in the ethanol solution of dye molecule (anionic dye, the dye of positive ion and neutral dye)
Test the result shows that: cationic MOF only has quick absorption property to anionic dye, and simultaneously to cation and neutral dye
Not similar absorption behavior.
The invention has the advantages that cationic metal-the organic frame is nontoxic and stable adsorbent material, for yin
Ionic dye has efficient absorption separating capacity.Provided by the invention preparation method is simple, short preparation period and easily recycling.
Ideal adsorption agent is provided for processing dye discoloration.
Detailed description of the invention
Fig. 1 is the poroid figure of metal-organic framework two dimension and three-dimensional perspective structure chart.
Fig. 2 is the powder diagram of the metal-organic framework.
Fig. 3 is absorption figure of the metal-organic framework to different dyes.
Fig. 4 is separation figure of the metal-organic framework to mixed dye.
Fig. 5 is that the dyestuff of the metal-organic framework discharges figure.
Specific embodiment
Example:
A kind of preparation method of the metal-organic framework materials, comprising the following steps:
1) (1,3- bis- (4- carboxyl phenyl) imidazoles villaumite (17.4mg), benzotriazole (5.9mg), zinc nitrate hexahydrate
(30mg) is added in the vial of 10ml, adds 3mLN, dinethylformamide solution.
2) sealing of above-mentioned vial is placed in 85 DEG C of baking oven, carries out incubating solvent thermal response, reacted 72 hours
Afterwards, strip light yellow crystal is obtained, yield is about 70%.
It 3) will be organic up to the metal-after above-mentioned light yellow crystal N,N-dimethylformamide and ethanol washing, drying
Frame material.
Gained metal-organic framework materials chemical formula is C60H39ClN14O10Zn4, with positive charge (1,3- bis- (4- carboxyl benzene
Base) imidazoles villaumite be main ligand, 1H- benzotriazole be assistant ligand, using solvent-thermal method, solvent N, N- dimethyl formyl
Amine aqueous solution synthesizes the metal-organic framework (NUM-4) of the poroid cationic of an example supermolecule.In NUM-4, zinc ion receives
Three nitrogen-atoms in benzotriazole form four core zinc clusters, pass through the carboxyl at diacid ligand both ends between four different core zinc clusters
Group, which is connected, becomes hexagonal cavernous structure.As shown in Fig. 1, which has biggish nano-pore in a axis direction
Road, hole size are about It is linked to be 3D by strong hydrogen bonding (C-HCl) between adjacent 2D layer to surpass
Molecular framework, porosity 52.8%.；Illustrate that obtained sample purity is very high in attached drawing 2, the decomposition temperature for being coordinated frame is 320
℃。
To the characterization of metal-organic framework materials obtained:
Crystal structure determination
The monocrystalline for choosing suitable size under the microscope, with the Mo-K through graphite monochromator monochromatization on single crystal diffractometer
Alpha ray, temperature 113K collect diffraction data in a manner of ω-φ.All diffraction datas carry out absorption school using SADABS program
Just.Cell parameter is determined with least square method.Data convert and structure elucidation use SAINT and SHELXTL program to complete respectively.
Whole non-hydrogen atom coordinates first are determined with difference function method and least square method, and obtain the hydrogen of main body frame with theoretical hydrogenation method
Then atom site carries out refine to crystal structure with least square method.Crystallography point diffraction data collection and structure refinement
Partial parameters see the table below 1.
Table 1: the crystal parameter table of the metal-organic framework
R1=Σ | | Fo|-|Fc||/Σ|Fo|；wR2=[Σ [w (Fo 2-Fc 2)2]/Σw(Fo 2)2]1/2.
Dye Adsorption, separation and release:
1) it is the frame material for exchanging 20mg ethyl alcohol first, is separately immersed in the different dyes molecule of 10ml 20ppm
Ethanol solution in.The ultraviolet test specification of liquid: the frame material, can be by 95% or more anionic dye within 720min
Absorption is complete, and to the dye of positive ion and neutral dye almost without absorption, (increase at any time, methyl as shown in Fig. 3
Orange, acid orange, methyl blue and Congo red absorbance are gradually reduced；The absorbance of methylene blue and Nile red remains unchanged).
2) secondly, the frame material that 20mg ethyl alcohol is exchanged, is separately immersed in isometric methyl orange/methylene blue,
In methyl orange/Nile red 10ml mixed solution.The ultraviolet test specification of liquid: frame material energy quick adsorption anion dye
Material stays cation and neutral dye in the solution, and (absorbance of increase at any time, methyl orange gradually drops as shown in Fig. 4
Low, the absorbance of methylene blue and Nile red is almost unchanged).
3) finally, the frame material for having adsorbed methyl orange and acid orange is immersed in 10ml saturation NH4The ethyl alcohol of Cl is molten
In liquid, over time, dyestuff can be released from frame quickly, and release rate is up to 99%, as shown in Fig. 5.
The Dye Adsorption experiment tested by TU-1950 ultraviolet-visible spectrometer, acquired results in the accompanying drawings,
Use Origin Software on Drawing.
Claims (5)
1. a kind of with the metal-organic framework materials for being selectively adsorbing and separating anionic dye performance, it is characterised in that: chemistry
Formula is C60H39ClN14O10Zn4, with it is positively charged (1,3- bis- (4- carboxyl phenyl) imidazoles villaumite for main ligand, 1-H benzo three
Nitrogen azoles is assistant ligand, and solvent is n,N-Dimethylformamide, and benzotriazole and metal zinc ion form four core Zn clusters, then lead to
It crosses diacid and connects into hexagonal cavernous structure, Magnetic Properties of Three-Dimensional Supramolecular Complex frame, hole are linked to be by strong hydrogen bonding between adjacent 2D layer
Gap rate is 52.8%；The metal-organic framework materials crystal belongs to monoclinic system, P21/mSpace group, cell parameter are respectively as follows: a
= 13.0559(2) Å, b = 37.1987(6) Å, c = 21.4712(2) Å, α=γ= 90o, β= 102.18o；Coordination
The decomposition temperature of frame is 320oC。
2. a kind of preparation method of metal-organic framework materials as described in claim 1, it is characterised in that the following steps are included:
1) by organic ligand, (1,3- bis- (4- carboxyl phenyl) imidazoles villaumite and benzotriazole and zinc nitrate hexahydrate are placed in
In 3ml n,N-Dimethylformamide solvent, this mixed solution is put into 10ml vial, ultrasonic 30min, is uniformly mixed；
2) sealing of above-mentioned vial is placed in 85 °C of baking ovens, incubating solvent thermal response is carried out, after reaction 72 hours
Obtain faint yellow strip crystal；
3) up to the metal-organic framework materials after above-mentioned yellow bulk crystals being washed with N,N-dimethylformamide, being dry.
3. the preparation method of metal-organic framework materials according to claim 2, it is characterised in that: (1, the 3- bis- (4-
Carboxyl phenyl) imidazoles villaumite, benzotriazole and zinc nitrate hexahydrate molar ratio be 1:1:2.
4. the preparation method of metal-organic framework materials according to claim 2, it is characterised in that: (1, the 3- bis- (4-
Carboxyl phenyl) imidazoles villaumite and solvent N,N-dimethylformamide amount ratio be 0.05 mM: 3.0 milliliter.
5. a kind of application of metal-organic framework materials as described in claim 1, it is characterised in that: the material is used for yin
The application of ionic dye selective absorption.
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| CN108084454A (en) * | 2018-01-12 | 2018-05-29 | 陕西理工大学 | A kind of sodium（I）Coordination polymer and preparation method and application |
| CN108384027B (en) * | 2018-05-07 | 2021-03-26 | 江西省科学院应用化学研究所 | Zinc-organic framework with acetylacetone fluorescent response and preparation method thereof |
| CN108993424B (en) * | 2018-07-18 | 2021-02-05 | 天津科技大学 | Preparation and regeneration method of porous lignin adsorbent |
| CN109351334A (en) * | 2018-09-12 | 2019-02-19 | 内蒙古大学 | A kind of methylene blue adsorption number material and its preparation method and application that water is stable |
| CN114450327B (en) * | 2019-08-29 | 2024-04-05 | 乔治亚技术研究公司 | Metal organic framework material and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531671A (en) * | 2009-04-15 | 2009-09-16 | 南开大学 | Micro-porous copper coordination polymer, preparation method and application thereof |
| CN102584901A (en) * | 2012-01-11 | 2012-07-18 | 南开大学 | Microporous nickel coordinate polymer as well as preparation method and application thereof |
-
2017
- 2017-08-11 CN CN201710683594.4A patent/CN107474060B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531671A (en) * | 2009-04-15 | 2009-09-16 | 南开大学 | Micro-porous copper coordination polymer, preparation method and application thereof |
| CN102584901A (en) * | 2012-01-11 | 2012-07-18 | 南开大学 | Microporous nickel coordinate polymer as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| A cage-based cationic body-centered tetragonal metal–organic framework: single-crystal to single-crystal transformation and selective uptake of organic dyes;Di-ming Chen等;《Chem. Commun.》;20141110;第51卷;第370-372页 |
| A cationic metal-organic framework based on {Zn4} cluster for rapid and selective adsorption of dyes;Weiwei He等;《Chinese Chemical Letters 》;20171013;第29卷;第857-860页 |
| Removal of hazardous organics from water using metal-organic frameworks (MOFs): Plausible mechanisms for selective adsorptions;Zubair Hasan等;《Journal of Hazardous Materials》;20140928;第283卷;第329-339页 |
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