CN103665015A - Mixed-ligand porous aluminum metal organic framework material and preparation method thereof - Google Patents
Mixed-ligand porous aluminum metal organic framework material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a mixed-ligand porous aluminum metal organic framework material and a preparation method thereof and mainly provides an aluminum-metal-containing organic framework material with a mixed ligand and adjustable pore structure, and a preparation method of the organic framework material. The preparation method comprises the following steps: dissolving reactants (inorganic aluminum salt and organic carboxylic acid) in an organic solvent, performing a crystallization reaction on the mixed solution for 3-90 hours at the temperature of 120-220 DEG C, taking out after naturally cooling, and performing suction filtration, washing, drying and roasting to obtain the metal organic framework material with porosity characteristic. The preparation method is simple in process and low in cost, and can be used for preparing the porous aluminum metal organic framework material under a mild condition. The structure of the prepared material with the mixed ligand can be adjusted, and the prepared material has wide application prospect in the aspects of adsorption, separation, catalysis and drug release.
Description
Technical field
The present invention relates to porous metal organic framework materials, be specifically related to a kind of mixed ligand porous aluminum metal organic frame material and preparation method thereof.
Background technology
Metal organic frame material is by metal ion and organic ligand, by covalent linkage or ionic linkage, interconnects, and forms coordination polymer materials.This class material has potential actual application value at gas storage, catalysis, separation, non-linear, magnetic, the aspect such as luminous, has caused various countries investigators' extensive concern, and such material had become the focus of new function material research in recent years.Recently, in the world, have the methods such as the logical hydrothermal method/solvent-thermal method of several study group to prepare the metal organic frame material that contains mixed ligand, these materials have good prospect aspect the storages such as hydrogen, carbonic acid gas, and such bill of material reveals excellent gas separating property.U.S. Yaghi in 2011, O.M. the group of teaching has reported the series metal organic framework materials containing zine ion class MOF-5 structure on < < Science > > magazine, this research shows that [Science 2010 by regulating part ratio can regulate material absorption property, 327 (5967), 846-850.].Within 2012, the virtuous grade of Sun Li people has reported the aluminum metal organic framework materials with high thermal stability that contains Isosorbide-5-Nitrae-naphthalic acid part, and this material has excellent gas adsorption selectivity.And research shows to use the solvent-thermal method of DMF to be better than hydrothermal method [Chem.Commun.2012,48 (5), 759-761.].
So far there are no relevant for the relevant report that contains Isosorbide-5-Nitrae-naphthalic acid mixed ligand porous aluminum metal organic frame material.This material has compared with bigger serface and higher thermostability, is so more conducive to gas adsorption with separated.
Summary of the invention
The object of the present invention is to provide a kind of mixed ligand porous aluminum metal organic frame material, and propose corresponding preparation method.
For achieving the above object, the technical solution used in the present invention is:
A mixed ligand porous aluminum metal organic frame material, it is the aluminiferous metals organic framework materials with vesicular structure, as follows preparation:
1) inorganic aluminate and organic carboxyl acid are dissolved in organic solvent, every 200mL organic solvent adds 2～30mmol inorganic aluminate and 5～30mmol organic carboxyl acid, and temperature of reaction is 120～220 ℃, and the crystallization time is 3～90 hours, naturally cools to room temperature;
Described inorganic aluminate class is aluminum nitrate, aluminum chloride, aluminum perchlorate; Organic acid is the amino terephthalic acid of 2-, Isosorbide-5-Nitrae-naphthalic acid;
2), by product collection, suction filtration, water or organic solvent washing, 30～120 ℃ of vacuum-dryings, then remove guest molecule 150～550 ℃ of roastings, makes porous mixed ligand aluminum metal organic framework materials; Its specific surface area is at 220-1200m
2/ g.
In described step 1) preparation method of porous aluminum metal organic frame material is solvent thermal synthesis method, inorganic aluminate and organic carboxyl acid press metallic cation and acid ion stoichiometric ratio (0.5～2) is added, it is 0 ~ 100% that organic carboxyl acid (the amino terephthalic acid of Isosorbide-5-Nitrae-naphthalic acid/2-) adds per-cent; Synthesis temperature is 120～220 ℃; Generated time is 3～90 hours.
In described step 1) inorganic aluminate class is aluminum nitrate, aluminum chloride, aluminum perchlorate; Organic acid is the amino terephthalic acid of 2-, Isosorbide-5-Nitrae-naphthalic acid, terephthalic acid; Solvent is DMF.
In described step 2) drying temperature is 30～120 ℃; Operating time is adjustable at 5～24 hours.150～550 ℃ of maturing temperatures; Operating time is adjustable at 4～15 hours.
Mixed ligand porous aluminum metal organic frame material provided by the present invention and preparation method's tool have the following advantages:
1. in the present invention, the part ratio of mixed ligand porous aluminum metal organic frame material is adjustable, and its specific surface area is at 220-1200m
2/ g.
2. synthesis technique is simple, and cost is lower.The present invention adopts solvent-thermal method synthetic, can obtain at short notice having the product of higher yields.
3. the present invention can prepare mixed ligand porous aluminum metal organic frame material under mild conditions; The porous material that has making has a wide range of applications at aspects such as absorption, separation, catalysis, drug release.
Accompanying drawing explanation
Fig. 1 is the powder X-ray RD diffraction curve of the mixed ligand porous aluminum metal organic frame material of specific embodiments of the invention 1.
Fig. 2 is the isothermal nitrogen adsorption curve of the mixed ligand porous aluminum metal organic frame material of specific embodiments of the invention 1.
Fig. 3 is the powder X-ray RD diffraction curve of the mixed ligand porous aluminum metal organic frame material of specific embodiments of the invention 2.
Fig. 4 is the isothermal nitrogen adsorption curve of the mixed ligand porous aluminum metal organic frame material of specific embodiments of the invention 2.
Fig. 5 is the powder X-ray RD diffraction curve of the mixed ligand porous aluminum metal organic frame material of specific embodiments of the invention 3.
Fig. 6 is the isothermal nitrogen adsorption curve of the mixed ligand porous aluminum metal organic frame material of specific embodiments of the invention 3.
Fig. 7 is hydrogen isothermal adsorption curve under the 77K of mixed ligand porous aluminum metal organic frame material of specific embodiments of the invention 1,2 and 3.
Fig. 8 is the 273K carbon dioxide isothermal adsorption curve of the mixed ligand porous aluminum metal organic frame material of specific embodiments of the invention 1,2 and 3.
Embodiment
To the powder X-ray RD diffraction experiment of described mixed ligand porous aluminum metal organic frame material, condition is: voltage: 40kV, electric current: 40mA.
To described mixed ligand porous aluminum metal organic frame material gas (N
2, H
2, CO
2) carry out on absorption property test Shi U.S. Kang Ta company (Quantachrome Instruments) Autosorb-1 type physical adsorption appearance, specific operation process is:
1) take 0.05～0.3g left and right sample, put into sample pool, in degassed station at 200 ℃ degassed 6～48 hours.
2) under 77K, carry out low temperature nitrogen and hydrogen adsorption test, use liquid nitrogen cooling.
3) under 273K, carry out carbonic acid gas absorption test, with mixture of ice and water, lower the temperature.
1) take 7.5g aluminum nitrate and 1.08g 1, amino terephthalic acid (the mol ratio: 5:15 of 4-naphthalic acid/2.72g 2-, add per-cent and count 25%) be dissolved in 195ml N, dinethylformamide, magnetic agitation is fully dissolved it, then mixing solutions is moved into the stainless steel cauldron of 3 100ml inner liner polytetrafluoroethylenes, in synthetic baking oven, 220 ℃ are reacted 3 days, naturally cool to room temperature.
2) by product suction filtration, and wash with DMF, 50 ℃ of oven dry, last, 200 ℃ of roastings 8 hours, obtain target product.
3) gas isothermal adsorption performance test: treatment condition be 200 ℃ degassed 24 hours.Test condition is 77K, nitrogen and hydrogen isothermal adsorption; 273K carbon dioxide absorption test.
1) take 7.5g aluminum nitrate and 2.18g 1, amino terephthalic acid (the mol ratio: 10:10 of 4-naphthalic acid/1.82g 2-, add per-cent and count 50%) be dissolved in 195ml N, dinethylformamide, magnetic agitation is fully dissolved it, then mixing solutions is moved into the stainless steel cauldron of 3 100ml inner liner polytetrafluoroethylenes, in synthetic baking oven, 220 ℃ are reacted 3 days, naturally cool to room temperature.
2) by product suction filtration, and wash with DMF, 50 ℃ of oven dry, last, 200 ℃ of roastings 8 hours, obtain target product.
3) gas isothermal adsorption performance test: treatment condition be 200 ℃ degassed 24 hours.Test condition is 77K, nitrogen and hydrogen isothermal adsorption; 273K carbon dioxide absorption test.
Embodiment 3
1) take 7.5g aluminum nitrate and 1.61g1, amino terephthalic acid (the mol ratio: 15:5 of 4-naphthalic acid/0.91g2-, add per-cent and count 75%) be dissolved in 195ml N, dinethylformamide, magnetic agitation is fully dissolved it, then mixing solutions is moved into the stainless steel cauldron of 3 100ml inner liner polytetrafluoroethylenes, in synthetic baking oven, 220 ℃ are reacted 3 days, naturally cool to room temperature.
2) by product suction filtration, and wash with DMF, 50 ℃ of oven dry, last, 200 ℃ of roastings 8 hours, obtain target product.
3) gas isothermal adsorption performance test: treatment condition be 200 ℃ degassed 24 hours.Test condition is 77K, nitrogen and hydrogen isothermal adsorption; 273K carbon dioxide absorption test.
Claims (8)
1. a mixed ligand porous aluminum metal organic frame material, is characterized in that: preparation as follows,
1) inorganic aluminate and organic carboxyl acid are dissolved in organic solvent, every 200mL organic solvent adds 2～30mmol inorganic aluminate and 5～30mmol organic carboxyl acid, and temperature of reaction is 120～220 ℃, and the crystallization time is 3～90 hours, naturally cools to room temperature;
Described inorganic aluminate is a kind of in aluminum nitrate, aluminum chloride, aluminum perchlorate; Organic acid is a kind of in the amino terephthalic acid of 2-, Isosorbide-5-Nitrae-naphthalic acid or two kinds;
2), by product collection, suction filtration, water or organic solvent washing, 30～120 ℃ of vacuum-dryings, then remove guest molecule 150～550 ℃ of roastings, makes mixed ligand porous aluminum metal organic frame material; Its specific surface area is at 220-1200m
2/ g.
2. according to mixed ligand porous aluminum metal organic frame material described in claim 1, it is characterized in that: in described step 1), inorganic aluminate adds than 0.5～2 by metallic cation and acid ion mole metering with organic carboxyl acid; In organic carboxyl acid, the interpolation molar percentage of the amino terephthalic acid of Isosorbide-5-Nitrae-naphthalic acid and 2-is 0 ~ 100%.
3. according to mixed ligand porous aluminum metal organic frame material described in claim 1, it is characterized in that: be 5～24 hours described time of drying, roasting time is 4～15 hours.
4. according to mixed ligand porous aluminum metal organic frame material described in claim 1, it is characterized in that: described organic solvent is DMF.
5. a preparation method for mixed ligand porous aluminum metal organic frame material described in claim 1, is characterized in that: preparation as follows:
1) inorganic aluminate and organic carboxyl acid are dissolved in organic solvent, every 200mL organic solvent adds 2～30mmol inorganic chromate salt and 5～30mmol organic carboxyl acid, and temperature of reaction is 120～220 ℃, and the crystallization time is 3～90 hours;
Described inorganic aluminate is a kind of in aluminum nitrate, aluminum chloride, aluminum perchlorate; Organic acid is a kind of in the amino terephthalic acid of 2-, Isosorbide-5-Nitrae-naphthalic acid or two kinds;
2), by product collection, suction filtration, water or organic solvent washing, 50～120 ℃ of vacuum-dryings, then remove guest molecule 150～550 ℃ of roastings, makes mixed ligand porous aluminum metal organic frame material.
6. according to the preparation method of mixed ligand porous aluminum metal organic frame material described in claim 5, it is characterized in that: in described step 1), inorganic aluminate adds than 0.5～2 by metallic cation and acid ion mole metering with organic carboxyl acid; In organic carboxyl acid, the interpolation molar percentage of the amino terephthalic acid of Isosorbide-5-Nitrae-naphthalic acid and 2-is 0 ~ 100%.
7. according to the preparation method of mixed ligand porous aluminum metal organic frame material described in claim 5, it is characterized in that: be 5～24 hours described time of drying; Roasting time is 4～15 hours.
8. according to the preparation method of mixed ligand porous aluminum metal organic frame material described in claim 5, it is characterized in that: described organic solvent is DMF.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437387A (en) * | 2014-11-25 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Metal-organic framework structure membrane material with high CO2/CH4 separating performance and preparation method thereof |
| CN105131025A (en) * | 2015-07-24 | 2015-12-09 | 郑州轻工业学院 | Micro-pore aluminum-based metal-organic framework material and preparation method thereof |
| CN108484929A (en) * | 2018-06-11 | 2018-09-04 | 天津城建大学 | A kind of metal organic frame synthesis MIL-53 (Al)-AO based on amidoxime2Preparation method |
| CN110078931A (en) * | 2019-04-12 | 2019-08-02 | 浙江大学 | A kind of organic framework materials and purposes |
| CN112608343A (en) * | 2020-12-21 | 2021-04-06 | 合肥水泥研究设计院有限公司 | Preparation method of sludge-based metal organic framework material |
| CN115322060A (en) * | 2021-05-10 | 2022-11-11 | 中国科学院大连化学物理研究所 | Application of MIL-53 aluminum-based metal organic framework material as stabilizer |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437387A (en) * | 2014-11-25 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Metal-organic framework structure membrane material with high CO2/CH4 separating performance and preparation method thereof |
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| CN108484929A (en) * | 2018-06-11 | 2018-09-04 | 天津城建大学 | A kind of metal organic frame synthesis MIL-53 (Al)-AO based on amidoxime2Preparation method |
| CN110078931A (en) * | 2019-04-12 | 2019-08-02 | 浙江大学 | A kind of organic framework materials and purposes |
| CN112608343A (en) * | 2020-12-21 | 2021-04-06 | 合肥水泥研究设计院有限公司 | Preparation method of sludge-based metal organic framework material |
| CN115322060A (en) * | 2021-05-10 | 2022-11-11 | 中国科学院大连化学物理研究所 | Application of MIL-53 aluminum-based metal organic framework material as stabilizer |
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