CN113667134A - Low-cost, rapid and universal green preparation method of stable metal organic framework material - Google Patents
Low-cost, rapid and universal green preparation method of stable metal organic framework material Download PDFInfo
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Abstract
A low-cost, quick and universal green preparation method for a stable metal organic framework material belongs to the technical field of crystalline state porous material preparation. According to the method, MOFs are rapidly synthesized at low temperature without adding an acidic regulator by adding corresponding crystal seeds and only using water as a solvent. The method has wide applicability to various water-stable MOFs, and can solve the problems of high pollution and high risk in the synthesis process of the MOFs to a certain extent. The method has application potential in the field of macroscopic preparation of MOFs materials.
Description
Technical Field
The invention belongs to the technical field of crystalline materials, and relates to a preparation method of a novel Metal Organic Framework (MOF), which is characterized in that the MOFs can be rapidly synthesized at low temperature without adding an acidic regulator by only using water as a solvent.
Background
Metal-organic frameworks (MOFs) are crystalline porous materials formed by connecting Metal ions or Metal clusters and organic ligands through coordination bonds, and have excellent properties such as high specific surface area and adjustable pore diameter. Has potential application value in a plurality of fields. However, the practical application of MOFs materials is very limited to date after more than 20 years of development. The current complicated, low-yield, high-cost, high-pollution and high-risk production modes adopted in the production of MOFs are main reasons. At present, a synthesis method commonly used in laboratories is a solvothermal synthesis method, and the common method is to uniformly mix, heat and stand raw materials in a solvent, and obtain the MOFs crystals after hours to days. N, N-Dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc) which are commonly used in the method have the defects of high toxicity, high price, flammability, teratogenicity and the like, are used in a small amount by researchers trained in a laboratory with good ventilation, can control the harm of the N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), but are directly amplified to be used on an industrial scale, and have great potential hazards. In addition, regulators such as formic acid, hydrofluoric acid and the like are commonly used in the synthesis of the MOFs at present, and have certain harm to the health of equipment and workers. Therefore, the development of a new method for synthesizing the MOFs with high speed, greenness, universality and low cost has important significance for future macro preparation and commercialization of the MOFs, environmental protection and improvement of the working environment of industrial workers. The harm can be reduced by using a green solvent (such as water and the like) and not using a strong corrosive volatile regulator (formic acid, hydrofluoric acid, trifluoroacetic acid and the like) in the synthesis of the MOFs, but the main problems faced at present are that many MOFs tend to grow undesirable crystal nuclei in water at low temperature, even cannot form the crystal nuclei, so that the required structures cannot grow out, many MOFs with excellent performance are unstable in water, and only more limited MOFs are reported to be synthesized in water without depending on an acidic regulator. We can skip the nucleation phase by adding foreign nuclei, i.e., can synthesize many water-stable MOFs that could not be synthesized in water. The method skillfully avoids the problem of difficult nucleation in water, directly enters the crystal growth stage to realize rapid green synthesis, and simultaneously avoids expensive and dangerous organic solvents and regulators, thereby achieving the purpose of preparing the MOFs safely at low cost.
Disclosure of Invention
The invention aims to provide a preparation method of a stable carboxylic acid-high-valence metal organic framework material, which can be used for low-cost, rapid and green synthesis of some water-stable MOFs.
The synthesis method of the invention has the following general synthesis steps:
(1) respectively weighing a certain amount of carboxylic acid ligand and NaOH, adding deionized water, and stirring until the carboxylic acid ligand and the NaOH are completely dissolved;
(2) weighing a certain amount of metal salt, adding the metal salt into the solution obtained in the step (1), and quickly stirring the solution until the suspension is uniformly dispersed;
(3) adding a proper amount of wet crystal seeds prepared in advance into the suspension obtained in the step (2) (the effect of the dried crystal seeds is not good in the partial MOFs synthesis process);
(4) and (3) continuously heating or stirring at normal temperature for reaction for several hours, wherein specific problems need to be specifically analyzed at specific temperature.
NaOH in the step (1) of the synthesis technical scheme ensures that the carboxylic acid ligand is completely dissolved and the pH of the reaction is adjusted to be alkaline, preferably 8-11. The mass percentage of the carboxylic acid ligand is 2-30%.
The seed crystal in the step (3) corresponds to a substance of a final product. The amount used is preferably 8-15% of the theoretical yield.
The reaction temperature of the step (4) is 25-80 ℃, and the reaction time is 4-6 h.
The carboxylic acid ligand of step (1) and the metal in the metal salt of step (2) may form a MOFs material.
According to the invention, on the premise of seed crystal assistance, various stable carboxylic acid ligand MOFs materials are prepared at low temperature, rapidly, greenly and at low cost, powder diffraction experiments show whether the synthesis is successful or not, and the quality of the product can be analyzed by testing the BET specific surface area. The powder diffraction pattern indicates successful synthesis, while the BET specific surface area test results show a higher quality of synthesis. The method is proved to be effective and have practical potential.
Drawings
FIG. 1 is a real photograph of the reaction apparatus of the present invention.
FIG. 2 is a graph of the diffraction pattern of an example MIL-53(Al) powder and a 77K nitrogen draw.
FIG. 3 is a powder diffraction pattern of example CAU-21 and accompanying 195K nitrogen uptake.
FIG. 4 is a graph of the powder diffraction pattern of example MIL-69 and the 77K nitrogen draw.
FIG. 5 is a powder diffraction pattern of example UiO-66 and a 77K nitrogen absorption plot.
FIG. 6 is a graph of an example MOF-801 powder diffraction pattern and 77K nitrogen uptake.
FIG. 7 is a graph of the diffraction pattern of the example CAU-10-H powder and 77K nitrogen uptake.
FIG. 8 is a powder diffraction pattern of example BUT-12 and a 77K nitrogen absorption plot.
FIG. 9 is a graph of the powder diffraction pattern of example BUT-18 and a 77K nitrogen draw.
FIG. 10 is a graph of the powder diffraction pattern of example BUT-66 and a 77K nitrogen draw.
FIG. 11 is an example of UiO-66-SO3H powder diffractogram and 77K nitrogen draw.
FIG. 12 is a graph of the diffraction pattern of an example MIL-101(Cr) powder and 77K nitrogen uptake.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
The seeds correspond to the material of the final product in the following examples. The amount used is preferably about 10% of the theoretical yield.
Example 1: (MIL-53(Al))
The first step is as follows: 332mg of terephthalic acid (H) were weighed out separately2BDC) ligand and 160mg NaOH were added to the flask 10 ml deionized water and stirred until completely dissolved
The second step is that: 965mg of AlCl is weighed3·6H2O, adding the mixture into the solution obtained in the first step, and quickly stirring the mixture until the suspension is uniformly dispersed;
the third step: and (3) adding a proper amount of wet crystal seeds (the drying crystal seeds have poor effect on part of MOFs synthesis process) obtained in advance into the suspension obtained in the step (2).
The fourth step: heating to 80 deg.C, stirring for 4 hr, centrifuging, and washing with water for 3 times to obtain the final product.
The fifth step: the product was activated and tested for powder diffraction and BET specific surface area. The results are shown in the attached drawings.
Example 2: (CAU-21)
The first step is as follows: 360mg of 4, 4-diphenyl ether dicarboxylic acid (H) was weighed out separately2ODB) ligand and 112mg NaOH were added to a flask with 10 ml deionized water and stirred until completely dissolved
The second step is that: weighing 336mg AlCl3·6H2O, adding the mixture into the solution obtained in the first step, and quickly stirring the mixture until the suspension is uniformly dispersed;
the third step: and (3) adding a proper amount of wet crystal seeds (the drying crystal seeds have poor effect on part of MOFs synthesis process) obtained in advance into the suspension obtained in the step (2).
The fourth step: heating to 80 deg.C, stirring for 4 hr, centrifuging, and washing with water for 3 times to obtain the final product.
The fifth step: the product was activated and tested for powder diffraction and BET specific surface area. The results are shown in the attached drawings.
Example 3: (MIL-69)
The first step is as follows: 432mg of 2, 6-naphthalenedicarboxylic acid (2, 6-H) were weighed out separately2NDC) ligand and 320mg NaOH were added to a flask with 15 ml deionized water and stirred until completely dissolved
The second step is that: weighing 500mg Al (NO)3)2·9H2O, adding the mixture into the solution obtained in the first step, and quickly stirring the mixture until the suspension is uniformly dispersed;
the third step: and (3) adding a proper amount of wet crystal seeds (the drying crystal seeds have poor effect on part of MOFs synthesis process) obtained in advance into the suspension obtained in the step (2).
The fourth step: heating to 80 deg.C, stirring for 4 hr, centrifuging, and washing with water for 3 times to obtain the final product.
The fifth step: the product was activated and tested for powder diffraction and BET specific surface area. The results are shown in the attached drawings.
Example 4: (UiO-66)
The first step is as follows: separately, 330mg of terephthalic acid (H) was weighed2BDC) ligand and 160mg NaOH were added to the flask with 15 ml deionized water and stirred until completely dissolved
The second step is that: weighing 348mg of ZrOCl2·8H2O, adding the mixture into the solution obtained in the first step, and quickly stirring the mixture until the suspension is uniformly dispersed;
the third step: and (3) adding a proper amount of wet crystal seeds (the drying crystal seeds have poor effect on part of MOFs synthesis process) obtained in advance into the suspension obtained in the step (2).
The fourth step: heating to 80 deg.C, stirring for 4 hr, centrifuging, and washing with water for 3 times to obtain the final product.
The fifth step: the product was activated and tested for powder diffraction and BET specific surface area. The results are shown in the attached drawings.
Example 5: (MOF-801)
The first step is as follows: 232mg of fumaric acid ligand and 160mg of NaOH are respectively weighed and added into a flask with 10 ml of deionized water and stirred until the fumaric acid ligand and the NaOH are completely dissolved
The second step is that: weighing 640mg ZrOCl2·8H2O, adding the mixture into the solution obtained in the first step, and quickly stirring the mixture until the suspension is uniformly dispersed;
the third step: and (3) adding a proper amount of wet crystal seeds (the drying crystal seeds have poor effect on part of MOFs synthesis process) obtained in advance into the suspension obtained in the step (2).
The fourth step: heating to 80 deg.c, stirring for 6 hr, centrifuging and washing for 3 times to obtain the product.
The fifth step: the product was activated and tested for powder diffraction and BET specific surface area. The results are shown in the attached drawings.
Example 6: (CAU-10-H)
The first step is as follows: 200mg of isophthalic acid ligand and 100mg of NaOH are respectively weighed and added into a flask with 10 ml of deionized water to be stirred until the isophthalic acid ligand and the NaOH are completely dissolved
The second step is that: weighing 290mg of AlCl3·6H2O, adding the mixture into the solution obtained in the first step, and quickly stirring the mixture until the suspension is uniformly dispersed;
the third step: and (3) adding a proper amount of wet crystal seeds (the drying crystal seeds have poor effect on part of MOFs synthesis process) obtained in advance into the suspension obtained in the step (2).
The fourth step: heating to 80 deg.C, stirring for 4 hr, centrifuging, and washing with water for 3 times to obtain the final product.
The fifth step: the product was activated and tested for powder diffraction and BET specific surface area. The results are shown in the attached drawings.
Example 7: (BUT-12)
The first step is as follows: separately, 64.45mg of 5' - (4-carboxyphenyl) -2', 4', 6' -trimethyl- [1,1 ':
3', 1' -triphenyl ] -4,4' -dicarboxylic acid ligand and 10mg NaOH are added into a flask with 10 ml deionized water and stirred until the ligand is completely dissolved
The second step is that: weighing 40mg ZrOCl2·8H2O, adding the mixture into the solution obtained in the first step, and quickly stirring the mixture until the suspension is uniformly dispersed;
the third step: and (3) adding a proper amount of wet crystal seeds (the drying crystal seeds have poor effect on part of MOFs synthesis process) obtained in advance into the suspension obtained in the step (2).
The fourth step: heating to 80 deg.C, stirring for 4 hr, centrifuging, and washing with water for 3 times to obtain the final product.
The fifth step: the product was activated and tested for powder diffraction and BET specific surface area. The results are shown in the attached drawings.
Example 8: (BUT-18)
The first step is as follows: 50mg of 5' - (4-carboxyphenyl) -2', 4', 6' -trimethyl- [1,1 ': 3', 1' -triphenyl ] -4,4' -dicarboxylic acid ligand and 25mg NaOH are added into a flask with 10 ml deionized water and stirred until completely dissolved
The second step is that: weighing 50mg AlCl3·6H2O, adding the mixture into the solution obtained in the first step, and quickly stirring the mixture until the suspension is uniformly dispersed;
the third step: and (3) adding a proper amount of wet crystal seeds (the drying crystal seeds have poor effect on part of MOFs synthesis process) obtained in advance into the suspension obtained in the step (2).
The fourth step: heating to 80 deg.C, stirring for 4 hr, centrifuging, and washing with water for 3 times to obtain the final product.
The fifth step: the product was activated and tested for powder diffraction and BET specific surface area. The results are shown in the attached drawings.
Example 9: (BUT-66)
The first step is as follows: 63.6mg of [1, 1': 3', 1' -triphenyl ] -4,4' -dicarboxylic acid ligand and 32mg NaOH are added into a flask with 10 ml deionized water and stirred until completely dissolved
The second step is that: weighing 64mg of ZrOCl2·8H2O, adding the mixture into the solution obtained in the first step, and quickly stirring the mixture until the suspension is uniformly dispersed;
the third step: and (3) adding a proper amount of wet crystal seeds (the drying crystal seeds have poor effect on part of MOFs synthesis process) obtained in advance into the suspension obtained in the step (2).
The fourth step: heating to 80 deg.C, stirring for 4 hr, centrifuging, and washing with water for 3 times to obtain the final product.
The fifth step: the product was activated and tested for powder diffraction and BET specific surface area. The results are shown in the attached drawings of the specification
Example 10: (UiO-66-SO)3H)
The first step is as follows: 210mg of 2-sulfoterephthalic acid monosodium ligand sodium salt and 80mg of NaOH are respectively weighed and added into a flask with 10 ml of deionized water to be stirred until the sodium salt and the NaOH are completely dissolved
The second step is that: weighing 250mg of ZrOCl2·8H2O, adding the mixture into the solution obtained in the first step, and quickly stirring the mixture until the suspension is uniformly dispersed;
the third step: and (3) adding a proper amount of wet crystal seeds (the drying crystal seeds have poor effect on part of MOFs synthesis process) obtained in advance into the suspension obtained in the step (2).
The fourth step: heating to 80 deg.C, stirring for 4 hr, centrifuging, and washing with water for 3 times to obtain the final product.
The fifth step: the product was activated and tested for powder diffraction and BET specific surface area. The results are shown in the attached drawings of the specification
Example 11: (MIL-101(Cr))
The first step is as follows: 33.2mg of terephthalic acid (H) were weighed out separately2BDC) ligand and 16mgNaOH were added to the flask with 10 ml deionized water and stirred until completely dissolved
The second step is that: 80mg of Cr (NO) is weighed3)3·9H2O, adding the mixture into the solution obtained in the first step, and quickly stirring the mixture until the suspension is uniformly dispersed;
the third step: and (3) adding a proper amount of wet crystal seeds (the drying crystal seeds have poor effect on part of MOFs synthesis process) obtained in advance into the suspension obtained in the step (2).
The fourth step: heating to 80 deg.C, stirring for 4 hr, centrifuging, and washing with water for 3 times to obtain the final product.
The fifth step: the product was activated and tested for powder diffraction and BET specific surface area. The results are shown in the attached drawings of the specification
Wherein the seed crystal synthesis step is referred to the following documents:
(T.Loiseau,C.Serre,C.Huguenard,G.Fink,F.Taulelle,M.Henry,T.Bataille and G.Ferey,Chemistry,2004,10,1373-1382.;
M.Kruger,A.K.Inge,H.Reinsch,Y.H.Li,M.Wahiduzzaman,C.H.Lin,S.L.Wang,G.Maurin and N.Stock,Inorg Chem,2017,56,5851-5862;
T.Loiseau,C.Mellot-Draznieks,H.Muguerra,G.Férey,M.Haouas and F.Taulelle,Comptes Rendus Chimie,2005,8,765-772.
F.Yang,H.Huang,X.Wang,F.Li,Y.Gong,C.Zhong and J.-R.Li,
Crystal Growth&Design,2015,15,5827-5833.
H.Furukawa,F.Gandara,Y.B.Zhang,J.Jiang,W.L.Queen,M.R.
Hudson and O.M.Yaghi,J Am Chem Soc,2014,136,4369-4381.
H.Reinsch,M.A.van der Veen,B.Gil,B.Marszalek,T.Verbiest,D.de Vos and N.Stock,Chemistry of Materials,2012,25,17-26.
L.H.Xie,X.M.Liu,T.He and J.R.Li,Chem,2018,4,1911-1927.
B.Wang,X.L.Lv,D.Feng,L.H.Xie,J.Zhang,M.Li,Y.Xie,J.R.Li and H.C.Zhou,J Am Chem Soc,2016,138,6204-6216.
J.Lv,Q.Chen,J.H.Liu,H.S.Yang,P.Wang,J.Yu,Y.Xie,Y.F.Wu and
J.R.Li,Inorg Chem,2021,60,1814-1822.)。
FIG. 1 is a real shot of the green synthesizer of the present invention
FIG. 2 example MIL-53(Al) powder diffractogram and 77K nitrogen adsorption plot
FIG. 3 example CAU-21 powder diffraction Pattern and 195K Nitrogen adsorption Pattern
FIG. 4 example MIL-69 powder diffractogram and 77K Nitrogen adsorption Pattern
FIG. 5 example UiO-66 powder diffraction Pattern and 77K Nitrogen adsorption Pattern
FIG. 6 example MOF-801 powder diffraction Pattern and 77K Nitrogen adsorption Pattern
FIG. 7 example CAU-10-H powder diffractogram and 77K nitrogen adsorption plot
FIG. 8 powder diffractogram of example BUT-12 and 77K nitrogen adsorption diagram
FIG. 9 example BUT-18 powder diffractogram and 77K nitrogen adsorption diagram
FIG. 10 example BUT-66 powder diffractogram and 77K nitrogen adsorption diagram
FIG. 11 example UiO-66-SO3H powder diffraction pattern and 77K nitrogen adsorption pattern
FIG. 12 example MIL-101(Cr) powder diffractogram and 77K nitrogen adsorption plot
The results show that the method has certain universality on MOFs materials stable in water, and is lower in cost, green, rapid and mild compared with the original synthesis scheme. The method is feasible for the 11 cases of MOFs materials with stable water, and lays a foundation for the industrial synthesis of the MOFs materials. The above is a preferred embodiment of the present invention, but the present invention should not be limited to the disclosure of this embodiment. Therefore, equivalents and modifications may be made thereto without departing from the spirit of the disclosure.
Claims (6)
1. A low-cost, rapid and universal green preparation method for a stable metal organic framework material is characterized by comprising the following steps:
(1) respectively weighing a certain amount of carboxylic acid ligand and NaOH, adding deionized water, and stirring until the carboxylic acid ligand and the NaOH are completely dissolved;
(2) weighing a certain amount of metal salt, adding the metal salt into the solution obtained in the step (1), and quickly stirring the solution until the suspension is uniformly dispersed;
(3) adding a proper amount of wet crystal seeds prepared in advance into the suspension obtained in the step (2) (the effect of the dried crystal seeds is not good in the partial MOFs synthesis process);
(4) the reaction is continued for several hours under heating or stirring at room temperature.
2. A low cost, rapid, universal, and green preparation method of a stable metal organic framework material according to claim 1, characterized in that NaOH should ensure complete dissolution of the carboxylic acid ligand in step (1) and adjust the reaction pH to alkaline, preferably pH 8-11.
3. The low-cost, rapid, universal, and green process for preparing a stable metal organic framework material according to claim 1, wherein the mass percent of the carboxylic acid ligand is 2-30%.
4. The low-cost, rapid, universal, and green process for preparing a stable metal organic framework material according to claim 1, wherein the seed of step (3) corresponds to the material of the final product; the amount used is preferably 8-15% of the theoretical yield.
5. The low-cost, rapid, general and green preparation method of a stable metal organic framework material according to claim 1, characterized in that the reaction temperature in the step (4) is 25 ℃ to 80 ℃ and the reaction time is 4h to 6 h.
6. The low-cost, rapid, universal, and green preparation method of a stable metal-organic framework material according to claim 1, wherein the carboxylic acid ligand of step (1) and the metal in the metal salt of step (2) form MOFs materials.
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---|---|---|---|---|
CN114395138A (en) * | 2022-02-17 | 2022-04-26 | 浙江大学 | Preparation method of microporous aluminum-based metal organic framework material with high specific surface area and water stability |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104892518A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Preparation method and application of porous nano metal organic framework material |
CN109174019A (en) * | 2018-11-07 | 2019-01-11 | 东莞华工创为生物科技有限公司 | A kind of preparation method and application of aluminium based metal organic backbone@absorbent charcoal composite material |
CN110172158A (en) * | 2019-04-25 | 2019-08-27 | 武汉理工大学 | A kind of preparation method of classifying porous metal-organic framework materials MIL-101 (Cr) |
CN112156659A (en) * | 2020-09-25 | 2021-01-01 | 南京工业大学 | M-gate metal organic framework membrane and preparation method and application thereof |
WO2021006964A1 (en) * | 2019-07-09 | 2021-01-14 | Exxonmobil Research And Engineering Company | Metal-organic framework materials comprising a pyrazolylcarboxylate ligand and methods for production thereof |
-
2021
- 2021-08-17 CN CN202110945968.1A patent/CN113667134A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104892518A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Preparation method and application of porous nano metal organic framework material |
CN109174019A (en) * | 2018-11-07 | 2019-01-11 | 东莞华工创为生物科技有限公司 | A kind of preparation method and application of aluminium based metal organic backbone@absorbent charcoal composite material |
CN110172158A (en) * | 2019-04-25 | 2019-08-27 | 武汉理工大学 | A kind of preparation method of classifying porous metal-organic framework materials MIL-101 (Cr) |
WO2021006964A1 (en) * | 2019-07-09 | 2021-01-14 | Exxonmobil Research And Engineering Company | Metal-organic framework materials comprising a pyrazolylcarboxylate ligand and methods for production thereof |
CN112156659A (en) * | 2020-09-25 | 2021-01-01 | 南京工业大学 | M-gate metal organic framework membrane and preparation method and application thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114395138A (en) * | 2022-02-17 | 2022-04-26 | 浙江大学 | Preparation method of microporous aluminum-based metal organic framework material with high specific surface area and water stability |
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