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 PDF

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CN105330681B
CN105330681B CN201510705960.2A CN201510705960A CN105330681B CN 105330681 B CN105330681 B CN 105330681B CN 201510705960 A CN201510705960 A CN 201510705960A CN 105330681 B CN105330681 B CN 105330681B
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rare earth
micropore
metal organic
organic anion
anion skeleton
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CN105330681A (en
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韩正波
高明亮
曹小漫
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Wuhu Digital Information Industrial Park Co., Ltd
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    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/223Solid 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
    • B01J20/226Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents

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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

A kind of rare earth cluster metal organic anion skeleton of micropore and its preparation method and application
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[Eu63-OH)8(BPDC)6(H2O)6]· 32DMF.The compound is by six core [Eu63-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[Eu63‐ OH)8(BPDC)6(H2O)6]·32DMF;The compound is by six core [Eu63‐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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CN106905534B (en) * 2017-01-17 2019-08-13 浙江大学 A kind of substep preparation method and application of high stable rare earth organic framework materials
CN107245149A (en) * 2017-06-21 2017-10-13 辽宁大学 The six core rare earth cluster metal-organic framework materials of one kind based on Eu (III) and its preparation method and application
CN107497402B (en) * 2017-09-25 2019-12-31 江苏大学 Water-stable dye adsorbent and preparation method thereof
CN109821574B (en) * 2019-02-18 2021-07-30 河海大学 Europium-based metal organic framework material Eu-MOF, preparation method thereof and Congo red dye photocatalytic degradation method
CN109821576B (en) * 2019-02-18 2021-07-27 河海大学 Dysprosium-based metal organic framework material Dy-MOF, preparation method thereof and methylene blue dye photocatalytic degradation method
CN109821575B (en) * 2019-02-18 2021-07-30 河海大学 Terbium-based metal organic framework material Tb-MOF, preparation method thereof and methylene blue dye photocatalytic degradation method
CN110560004A (en) * 2019-09-19 2019-12-13 西北师范大学 Eu-MOF complex, synthesis thereof and application of Eu-MOF complex in adsorption of organic dye in wastewater

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