CN105330681B - A kind of rare earth cluster metal organic anion skeleton of micropore and its preparation method and application - Google Patents
A kind of rare earth cluster metal organic anion skeleton of micropore and its preparation method and application Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 41
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 41
- 150000002891 organic anions Chemical group 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000975 dye Substances 0.000 claims abstract description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 17
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical class C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract 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 claims description 13
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- -1 4,4 '-biphenyl dicarboxylic acid Oxygen Chemical compound 0.000 claims 2
- 150000001450 anions Chemical class 0.000 claims 1
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 150000002892 organic cations Chemical class 0.000 description 4
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 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 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 2
- LGLFFNDHMLKUMI-UHFFFAOYSA-N crystal violet cation Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=C1C=CC(=[N+](C)C)C=C1 LGLFFNDHMLKUMI-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LCALVNLSKDINOK-UHFFFAOYSA-N C(=O)O.FC=1C=CC=CC1 Chemical group C(=O)O.FC=1C=CC=CC1 LCALVNLSKDINOK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical group [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process 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
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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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
- 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]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- Chemical & Material Sciences (AREA)
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The present invention relates to rare earth cluster metal organic anion skeleton of a kind of micropore and its preparation method and application.The technical scheme of use is:RE(NO3)3, 4,4' biphenyl dicarboxylic acids, o-fluorobenzoic acid, N, N dimethylformamides and ethanol added in container, under normal temperature, stirring;It is put into baking oven, under 300 400K, is kept for 12 days after container is sealed;It is slowly cooled to room temperature, stands 20 30h, obtain crystal;With N, the washing of N dimethylformamides is filtered, dries, obtain target product.The rare earth cluster metal organic anion skeleton of micropore prepared by the present invention can be adsorbed as adsorbing base to cationic organic dyestuff, efficient selective separation Cationic organic dyes.
Description
Technical field
The present invention relates to a kind of metal organic anion skeleton and its preparation method and application, specifically, it is related to one kind
Rare earth cluster metal organic anion skeleton based on micropore with cation exchange function and preparation method thereof, and its to organic
The absorption and separation application of dyestuff.
Background technology
In host-guest chemistry field, metal organic framework (MOFs) as a kind of novel molecular functional material, on it
Research span inorganic chemistry, organic chemistry, physical chemistry, materials chemistry, crystal engineering, topology, supramolecular chemistry and
Multiple ambits such as Coordinative Chemistry.The product intersected as multidisciplinary field, the design synthesis of metal organic framework compound
And performance study has developed into one of Recent study very active field.Recently, powered MOFs can be lured by electric charge
Lead ion exchange process and increasingly cause the interest of researcher, this makes rear synthetic modification process simple and controllable.At these
In MOFs, the MOFs of anionic is often produced during neutral organic ligand and metal ion build skeleton, therefore, is needed
The cation beyond skeleton is wanted to play a part of charge balance.Counter cation is generally taken up in the hole of skeleton, with metal from
Son is not coordinated or has weak coordination.This material provides one to build the cation receptor based on cation exchange
Unique chance.On the other hand, inorganic-organic hybridization MOFs has diversified internal microenvironment, can be as remarkably
Material of main part is used to recognizing and separating cationic system, and this process will depend on size, geometric shape and the combination in MOFs holes
Ability.Compared with neutral backbone, the MOFs researchs of anionic are very limited.
China has been global maximum DYE PRODUCTION state, and annual dyestuff yield is up to 150000 tons, and environmental pollution phenomenon is non-
Chang Yanchong, increasingly sophisticated with dye structure, dyeing is continued to develop, and performance is increasingly stablized, these waste water from dyestuff
Processing it is more complicated.Different types of waste water from dyestuff is handled using different sewage disposal technologies, sewage qualified discharge is realized
Or recycle, the problem of be current in the urgent need to address.
The content of the invention
The purpose of the present invention is, by the use of six core Eu clusters as metal node, to be matched somebody with somebody using 4,4 '-biphenyl dicarboxylic acid as organic
Body, at a certain temperature, a kind of rare earth cluster metal organic anion skeleton of micropore is synthesized using the method for solvent heat.
The technical solution adopted by the present invention is:A kind of rare earth cluster metal organic anion skeleton of micropore, including following step
Suddenly:
1) by RE (NO3)3, 4,4 '-biphenyl dicarboxylic acid, o-fluorobenzoic acid, N,N-dimethylformamide and ethanol add container
In, under normal temperature, stir;Wherein, RE is rare earth metal.It is preferred that, RE (NO3)3For Eu (NO3)3.In molar ratio, Eu (NO3)3:
4,4 '-biphenyl dicarboxylic acid:O-fluorobenzoic acid=1:1-1.5:3-3.5.
2) it is put into baking oven, under 300-400K, is kept for 1-2 days after container is sealed;It is preferred that, heating rate is 2-8
℃·min-1。
3) it is slowly cooled to room temperature, stands 20-30h, obtain crystal;It is preferred that, the rate of temperature fall being slowly cooled to room temperature
For 2-8 DEG C of h-1, and at least 24 hours are stood at room temperature.
4) crystal is washed with DMF, filtered, dried, obtain target product.
The beneficial effects of the invention are as follows:The rare earth cluster metal organic anion skeleton of micropore prepared by the present invention can conduct
Material of main part is applied to the rear synthesis field of host-guest chemistry.The rare earth cluster metal organic anion skeleton of prepared micropore can
To be adsorbed as adsorbing base to cationic organic dyestuff, efficient selective separation Cationic organic dyes.The present invention
Micropore rare earth cluster metal organic anion skeleton preparation method it is simple, have great application prospect.
Brief description of the drawings
Fig. 1 is the synthesis schematic diagram of the rare earth cluster metal organic anion skeleton of micropore of the present invention.
Fig. 2 is the XRD of the rare earth cluster metal organic anion skeleton of micropore of the present invention.
Fig. 3 a be micropore of the present invention a kind of cage of rare earth cluster metal organic anion skeleton () show
It is intended to.
Fig. 3 b be micropore of the present invention a kind of cage of rare earth cluster metal organic anion skeleton () show
It is intended to.
Fig. 3 c be micropore of the present invention rare earth cluster metal organic anion skeleton duct () schematic diagram.
Fig. 4 is the cage skeleton structure schematic diagram of the rare earth cluster metal organic anion skeleton of micropore of the present invention.
Fig. 5 is that the rare earth cluster metal organic anion skeleton Selective Separation methyl orange of micropore of the present invention has with methylene blue
The ultraviolet-visible spectrogram of engine dyeing material.
Fig. 6 is rare earth cluster metal organic anion skeleton Selective Separation tonyred and methine of the present invention based on micropore
The ultraviolet-visible spectrogram of blue organic dyestuff.
Fig. 7 is rare earth cluster metal organic anion skeleton Selective Separation crystal violet and methine of the present invention based on micropore
The ultraviolet-visible spectrogram of blue organic dyestuff.
Embodiment
The rare earth cluster metal organic anion skeleton of the micropore of embodiment 1
By 0.0225mmol Eu (NO3)3, the 4 of 0.0225mmol, 4 '-biphenyl dicarboxylic acid, 0.0675mmol adjacent fluorobenzene
Formic acid, 2ml DMF (DMF), 0.5ml ethanol adds volume in 5ml vial, under normal temperature, to stir
Mix 30 minutes.Vial good seal is put into baking oven.Heating makes the temperature of baking oven reach 378K from room temperature, and heating rate is 5
℃·min-1, it is incubated 36 hours at this temperature.With 5 DEG C of h-1Rate of temperature fall be slowly cooled to room temperature, obtain faint yellow vertical
Square bulk crystal;With N, the washing of N '-dimethyl formamide (DMF) solution, filtering are simultaneously dried in atmosphere, and as target product is micro-
The rare earth cluster metal organic anion skeleton in hole, yield is 68%.
The structure of the rare earth cluster metal organic anion skeleton for the micropore that the present invention is synthesized as shown in figs 2-4, the crystal knot
Structure belongs to cubic system, and space group is Fm-3m.Molecular formula is:[(CH3)2NH2]2[Eu6(μ3-OH)8(BPDC)6(H2O)6]·
32DMF.The compound is by six core [Eu6(μ3-OH)8(O2C–)6] as node, tied by the three-dimensional of dicarboxylates bridging
Structure.Cation [(CH3)2NH2]+In the duct for being located at the MOF as counter ion counterionsl gegenions.Each 4,4 '-biphenyl dicarboxylic acid part and four
Eu 3+Ion coordination, six Eu3+Ion and six oxygen come from the carboxyl of 4,4 '-biphenyl dicarboxylic acid and six μ3- OH matches somebody with somebody
Position.Along b- direction of principal axis, the structure has two kinds of different cage structures, and the size of cage is
And there is a duct
A kind of rare earth cluster metal organic anion skeleton selective absorption organic dyestuff of the micropore of embodiment 2
Method:The rare earth cluster metal organic anion skeleton of the micropore prepared using embodiment 1 is as adsorbing base to mixing
Organic dyestuff is adsorbed.
1) take organic anionic dyes methyl orange and organic cation dye methylene blue to be dissolved in DMF solution, obtain first
The concentration of base orange and methylene blue is respectively 5 × 10-5M mixed dye solution.
Mixed dye solution 5ml is taken, the rare earth cluster metal organic anion skeleton crystal 20mg of micropore is added, at room temperature
Immersion.The change of dye strength in mixed dye solution is detected with uv-vis spectra.As a result as shown in figure 5, in figure peak value from
Top to bottm is followed successively by 0min, 10min, 30min, 1h, 2h, 3h, 4h, 6h, 24h.As seen from Figure 5, time first in mixed dye solution
The blue feature peak intensity in 650nm of base is gradually reduced, and methyl orange is constant in 420nm feature peak intensity.This explanation present invention
The crystal structure of rare earth cluster metal organic anion skeleton of micropore a kind of there is good selective absorption to methylene blue.
The rare earth cluster metal organic anion skeleton of the micropore of the present invention is in 6h, and the adsorption rate to methylene blue reaches
75%, in 24h, adsorption rate has reached 98%.
2) take organic zeroth order dyestuff tonyred and organic cation dye methylene blue to be dissolved in DMF solution, obtain the Sudan
Red and methylene blue concentration is respectively 5 × 10-5M mixed dye solution.
Mixed dye solution 5ml is taken, the rare earth cluster metal organic anion skeleton crystal 20mg of micropore is added, at room temperature
Immersion.The change of dye strength in mixed dye solution is detected with uv-vis spectra.As a result as shown in fig. 6, in Fig. 6 peak value from
Top to bottm is followed successively by 0min, 10min, 30min, 1h, 2h, 3h, 4h, 5h, 7h, 24h.As seen from Figure 6, it is secondary in mixed dye solution
Methyl blue is gradually reduced in 650nm feature peak intensity, and tonyred is constant in 480nm feature peak intensity.This illustrates this hair
The crystal structure of the rare earth cluster metal organic anion skeleton of bright micropore has good selective absorption to methylene blue.
3) take organic cation dye crystal violet and organic cation dye methylene blue to be dissolved in DMF solution, tied
The concentration of crystalviolet and methylene blue is respectively 5 × 10-5M mixed dye solution.
Mixed dye solution 5ml is taken, the rare earth cluster metal organic anion skeleton crystal 20mg of micropore is added, at room temperature
Immersion.The change of dye strength in mixed dye solution is detected with uv-vis spectra.As a result as shown in fig. 7, in Fig. 7 peak value from
Top to bottm is followed successively by 0min, 10min, 30min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 24h.As seen from Figure 7, mixed dye solution
Middle methylene blue is gradually reduced in 650nm feature peak intensity, and crystal violet is constant in 600nm feature peak intensity.This explanation
The crystal structure of the rare earth cluster metal organic anion skeleton of the micropore of the present invention has selectivity suction well to methylene blue
It is attached.
Claims (8)
1. a kind of rare earth cluster metal organic anion skeleton of micropore, it is characterised in that:The rare earth cluster metal of described micropore has
Machine anion frame, the crystal structure belongs to cubic system, and space group is Fm-3m;Molecular formula is:[(CH3)2NH2]2[Eu6(μ3‐
OH)8(BPDC)6(H2O)6]·32DMF;The compound is by six core [Eu6(μ3‐OH)8(O2C–)6] as node, by dicarboxylic acids
The three-dimensional structure of part bridging, cation [(CH3)2NH2]+In the duct for being located at the MOF as counter ion counterionsl gegenions, each 4,
4 '-biphenyl dicarboxylic acid part and four Eu3+Ion coordination, six Eu3+Ion and six come from 4,4 '-biphenyl dicarboxylic acid
Oxygen and six μ on carboxyl3- OH is coordinated, and along b- direction of principal axis, the structure has two kinds of different cage structures, the size of cage
ForAnd there is a duct
2. a kind of preparation method of the rare earth cluster metal organic anion skeleton of micropore described in claim 1, it is characterised in that:
Preparation method comprises the following steps:
1) by Eu (NO3)3, 4,4 '-biphenyl dicarboxylic acid, o-fluorobenzoic acid, DMF and ethanol are added in container,
In under normal temperature, stir;Wherein, RE is rare earth metal;
2) it is put into baking oven, under 300-400K, is kept for 1-2 days after container is sealed;
3) it is slowly cooled to room temperature, stands 24-30h, filtering obtains crystal;
4) crystal is washed with DMF, is filtered, and is dried, is obtained target product.
3. a kind of preparation method of the rare earth cluster metal organic anion skeleton of micropore according to claim 2, its feature
It is:In molar ratio, Eu (NO3)3:4,4 '-biphenyl dicarboxylic acid:O-fluorobenzoic acid=1:1-1.5:3-3.5.
4. a kind of preparation method of the rare earth cluster metal organic anion skeleton of micropore according to claim 2, its feature
It is:Step 2) in, it is put into after container is sealed in baking oven, heating rate is 2-8 DEG C of min-1。
5. a kind of preparation method of the rare earth cluster metal organic anion skeleton of micropore according to claim 2, its feature
It is:Step 3) in, the described rate of temperature fall being slowly cooled to room temperature is 2-8 DEG C of h-1。
6. the rare earth cluster metal organic anion skeleton of the micropore described in claim 1 is as adsorbing base in Liquidity limit type
Application in organic dyestuff.
7. application according to claim 6, it is characterised in that method is as follows:In the N containing cationic organic dyestuff,
In dinethylformamide solution, the rare earth cluster metal organic anion skeleton of the micropore described in claim 1 is added, soak,
Absorption.
8. the application according to claim 6 or 7, it is characterised in that:Described cationic organic dyestuff is methylene blue.
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CN106397467B (en) * | 2016-08-31 | 2018-07-06 | 北京化工大学 | A kind of metal-organic framework functional fluorescence material, preparation method and applications |
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