CN107828065A - A kind of In MOFs materials and its production and use - Google Patents

A kind of In MOFs materials and its production and use Download PDF

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Publication number
CN107828065A
CN107828065A CN201710899522.3A CN201710899522A CN107828065A CN 107828065 A CN107828065 A CN 107828065A CN 201710899522 A CN201710899522 A CN 201710899522A CN 107828065 A CN107828065 A CN 107828065A
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China
Prior art keywords
mofs materials
mofs
solution
organic
indium
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Pending
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CN201710899522.3A
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Chinese (zh)
Inventor
王海营
高桂梅
刘洁
刘会艳
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Jiangsu Normal University
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Jiangsu Normal University
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Priority to CN201710899522.3A priority Critical patent/CN107828065A/en
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Abstract

The invention discloses a kind of In MOFs materials and its production and use, prepare with indium In (III) as secondary construction unit, tetrabasic carboxylic acid 5 (3 containing amido link modification, 5 dicarboxyl benzamido bases) M-phthalic acid (H4L1) is organic ligand, Dye Adsorption experiment proves, the In MOFs materials have the advantages that adsorption efficiency is high and stability is good as adsorbent, and can the dyestuff such as the methylene blue in absorbing organic solvent, methyl orange, rhodamine B in actual use.

Description

A kind of In-MOFs materials and its production and use
Technical field
The present invention relates to a kind of preparation method of In-MOFs materials and they as adsorbent to dyestuff in organic solvent（Such as Methylene blue, methyl orange and rhodamine B etc.）Study on adsorption properties.This In-MOFs materials as adsorbent there is absorption to hold Amount is high, and dyestuff removal efficiency is high, small, simple, the safe and cost-effective advantage of dosage.
Technical background
Metal-organic framework materials (Metal-Organic Frameworks, MOFs), also referred to as Porous coordination polymer That is (Porous Coordination Polymers, PCPs), it is a kind of porous complex material with periodic network structure, Various organic ligands and secondary construction unit (SBUs) are contained in structure.It is adjustable due to part in MOFs structures and SBUs Property, there can be the MOFs materials in the duct of nano-scale by adjusted design, these ducts have adsorption property, can absorb one The fluorescent material and dyestuff of a little organic or inorganics.Dyestuff waste liquid is a kind of new environment problem occurred with industrial development simultaneously.Perhaps More dyestuffs are poisonous even carcinogenic, and most of poisonous dye substances are stable to light and oxidant, are not allowed It is degradable.Although oneself is through there is some processing methods, for example, biological treatment, film process, improved oxidation processes, electrochemical method and Adsorption treatment etc., but effect is not apparent.Therefore, the MOFs materials with significant adsorption property turn into for Dye Adsorption The focus of research.MOFs materials for adsorbing organic dyestuff are mostly ZIF-8, Fe-MIL-101, Al-MOF, Cr-MOF at present Deng MOFs materials.Indium is the A races element of period 5 the IIIth, and indium can take hexa-coordinate, seven coordinations even eight-coordinate, Jin Erneng Enough and organic ligand forms higher stability In-MOFs materials.Meanwhile adsorb to have there has been no In-MOFs materials at present The report and patent of engine dyeing material.
The present inventor by solvent structure In-MOFs materials, and using the material be adsorbent be used for be adsorbed with engine dyeing Material（Such as methylene blue, methyl orange and rhodamine B）, it is found that the In-MOFs materials have skeleton stable, after adsorpting dye molecule Still keep stable skeleton（See Fig. 2）.In addition the In-MOFs materials and ZIF-8, Fe-MIL-101, Al-MOF, Cr-MOF etc. MOFs materials absorption dyestuff is compared, safe efficient, low cost and other advantages few with dosage.
The content of the invention
It is an object of the invention to be secondary construction unit by indium In (III), the tetrabasic carboxylic acid 5- containing amido link modification (3,5- dicarboxyl benzamidos base) M-phthalic acid (H4L1) it is organic ligand, a kind of In-MOFs materials are synthesized, deeply On the basis of studying its absorption property, it is found that the In-MOFs materials are preferable to the absorption property of organic dyestuff, provide accordingly a kind of Application of the In-MOFs materials as sorbing material（By taking methylene blue as an example）, while the preparation side of the In-MOFs materials is provided Method.
Technical scheme is as follows：
In-MOFs preparation method, comprises the following steps：
1) indium salts are dissolved in the organic solvent containing carbonyl, indium salts solution is made.
2) tetracarboxylic organic ligand is dissolved in the organic solvent containing carbonyl, ligand solution is made.
3) heating response under confined conditions is transferred to after indium salts solution and ligand solution being mixed into ultrasound, and will be reacted Product filters, washs, is dried to obtain In-MOFs.
4) indium salts are In (NO3)3·6H2O, organic solvent are DMF, DMA, second Any one mixed solvent that either any of which and N,N-dimethylformamide are formed in alcohol and acetonitrile.
5) temperature of heating response is 85-100oC, heating response time are 12-24 h.
Brief description of the drawings
The structural topology figure of Fig. 1 In-MOFs materials
The XRD powder diagrams of Fig. 2 In-MOFs materials
The ultraviolet spectrometry spectrum canonical plotting of Fig. 3 methylene blues
The ultraviolet spectrometry spectrogram of the In-MOFs materials absorption methylene blue of Fig. 4 different qualities
The ultraviolet spectrometry spectrogram of In-MOFs materials absorption methylene blue under Fig. 5 different time sections.
Embodiment
The present invention is further described by following examples, but should be noted that the scope of the present invention is not implemented by these Any restrictions of example.
Embodiment 1：
In the reaction of In-MOFs materials is prepared using the tetracid part of amide group modification and metal In (III) reactions, temperature Degree, the mol ratio of raw material and the time of reaction have an impact to phase purity, yield and the adsorption effect of product（It is shown in Table 1）.With Body H4L1With In (NO3)3·6H2In O reaction, if the optimum mole ratio of part and metal salt is 1:3, temperature 90oC, during reaction Between be 12 h, the topological structure and XRD powder diffractions of product are shown in Fig. 1 and Fig. 2.
Embodiment 2：
Under 652 nm wavelength, determine the ultraviolet absorptivity of the methylene blue methanol solution of various concentrations respectively, according to concentration and Ultraviolet absorptivity draws canonical plotting（See Fig. 3）.
Embodiment 3：
It is 8*10 in 10 mL concentration-5In mg/L methylene blue methanol solution, the mg of In-MOFs materials 5,10 are separately added into Mg, 15 mg and 20 mg, after adsorption reaction 15min, pass through ultraviolet specrophotometer（See Fig. 4）, calculate methylene blue solution Clearance, after adding the mg of In-MOFs materials 20, the clearance of methylene blue is 88.3%
Embodiment 3：
It is 8*10 in 10 mL concentration-5In mg/L methylene blue methanol solution, the mg of In-MOFs materials 10 is added, is existed respectively After the min of adsorption reaction 10,15 min, 20 min, 40 min and 60 min, pass through ultraviolet specrophotometer（See Fig. 5）, calculate The clearance of methylene blue solution, it is found that in 60 min, the clearance of methylene blue can reach 82.4%
Embodiment 5：To the practical application of the dyestuffs such as absorption methyl orange, rhodamine B
Using the assay method established before, had shown that by the absorption research to dyestuffs such as methyl orange in methyl alcohol, rhodamine Bs Two kinds of In-MOFs materials have the advantages that adsorption efficiency is high and stability is good as adsorbent, and can be in actual Dye Adsorption Use.
The reaction condition and product purity of table 1In-MOFs materials
Form can be seen that the mol ratio of its raw material 1:3, which have reached an extraordinary condition name, has very prominent effect Fruit.

Claims (5)

1. a kind of preparation method of In-MOFs materials, it is characterized in that,
Indium salts are dissolved in the organic solvent containing carbonyl, indium salts solution is made；
Tetracarboxylic organic ligand is dissolved in the organic solvent containing carbonyl, ligand solution is made；
Indium salts solution and ligand solution are mixed heating response under confined conditions is transferred to after ultrasound, and by reacted product mistake Filter, wash, be dried to obtain In-MOFs.
2. the preparation method of the In-MOFs materials described in a kind of claim 1 according to claim 1, it is characterised in that
Indium salts are In (NO3)3·6H2O, organic solvent are DMF, DMA, ethanol and second Any one mixed solvent that either any of which and N,N-dimethylformamide are formed in nitrile.
3. the preparation method of the In-MOFs materials described in a kind of claim 1 according to claim 1, it is characterised in that
The temperature of heating response is 85-100oC, heating response time are 12-24 h.
4. a kind of In-MOFs materials, it is characterised in that prepare with indium In (III) as secondary construction unit, modified containing amido link Tetrabasic carboxylic acid 5- (3,5- dicarboxyl benzamidos base) M-phthalic acid (H4L1) it is organic ligand, the In-MOFs materials of synthesis With following structure：
。
5. application of the In-MOFs materials as claimed in claim 4 as sorbing material organic dyestuff in adsorbent solution.
CN201710899522.3A 2017-09-28 2017-09-28 A kind of In MOFs materials and its production and use Pending CN107828065A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111686694A (en) * 2019-03-15 2020-09-22 中国石油化工股份有限公司 Preparation method and application of MIL-101 material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101248034A (en) * 2005-08-22 2008-08-20 巴斯夫欧洲公司 Method for producing organometallic framework materials containing main group metal ions
CN104650125A (en) * 2015-03-13 2015-05-27 辽宁大学 InIII-based metal organic anion framework and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101248034A (en) * 2005-08-22 2008-08-20 巴斯夫欧洲公司 Method for producing organometallic framework materials containing main group metal ions
CN104650125A (en) * 2015-03-13 2015-05-27 辽宁大学 InIII-based metal organic anion framework and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MINGXING ZHANG, BIN LI, YUNZHI LI,ET.AL: "Finely tuning MOFs towards high performance in C2H2 storage: synthesis and properties of a new MOF-505 analogue with an inserted amide functional group", 《CHEM. COMMUN.》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111686694A (en) * 2019-03-15 2020-09-22 中国石油化工股份有限公司 Preparation method and application of MIL-101 material

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Application publication date: 20180323