CN104478907A - Preparation method of metal organic skeleton material - Google Patents
Preparation method of metal organic skeleton material Download PDFInfo
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- CN104478907A CN104478907A CN201410652749.4A CN201410652749A CN104478907A CN 104478907 A CN104478907 A CN 104478907A CN 201410652749 A CN201410652749 A CN 201410652749A CN 104478907 A CN104478907 A CN 104478907A
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- organic framework
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 25
- 239000012621 metal-organic framework Substances 0.000 claims description 23
- 239000013384 organic framework Substances 0.000 claims description 16
- 150000007524 organic acids Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 14
- 239000012917 MOF crystal Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000010189 synthetic method Methods 0.000 abstract description 6
- 239000012923 MOF film Substances 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 3
- 239000011259 mixed solution Substances 0.000 abstract 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000009931 pascalization Methods 0.000 abstract 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 36
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 18
- 235000019253 formic acid Nutrition 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004675 formic acid derivatives Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention provides a preparation method of a metal organic skeleton material. The preparation method comprises the following steps: (1) dissolving an organic carboxylic acid in water or an alcohol solution so as to form an organic carboxylic acid solution; (2) adding metal oxide powder into the organic carboxylic acid solution so as to form a metal salt solution; (3) adding an inorganic alkali solution into the metal salt solution so as to form a transparent mixed solution; and (4) standing the mixed solution so as to generate a metal organic skeleton crystal, or treating the mixed solution by using a solution-mode film formation method so as to form a metal organic skeleton film. The preparation method of the metal organic skeleton material provided by the invention is implemented without high temperature and high pressure processing, and MOF crystals can be quickly formed; MOF films can be prepared by using the solution-mode film formation method; and high-quality MOF crystal precipitates or films can be obtained, and the preparation method is simple in synthetic method, good in stability of preparation process, and low in cost, therefore, the preparation method is suitable for large-scale industrial production, and has a considerable application prospect.
Description
Technical field
The invention belongs to field of new, particularly relate to a kind of preparation method of metal-organic framework materials.
Background technology
Metallic organic framework (MOF), also claims mesoporous ligand polymer, is a kind of hybrid inorganic-organic crystalline material of novelty.It is by metal ion or the multinuclear bunch skeleton structure be formed by connecting by various informative organic coordination key, its aperture structure, size, functionally can pass through metal ion, and coordinate bond and mode of connection are controlled.Due to the specific surface area of MOF and aperture size controlled, the various fields such as atmosphere storage, medicine loading, molecular recognition, selective catalysis, ion-exchange, bio-sensing, photoelectric material, magneticsubstance and chip can be applied to.
The synthesis of usual MOF material is the crystalline material that preparation has certain physical strength on the carrier of porous or densification.Primary synthetic methods has 1, hydro-thermal (solvent) method.Metal-salt and organic ligand are being rendered in solvent by a certain percentage, is utilizing the coordination reaction that High Temperature High Pressure occurs.The generated time of this method is short, can solve the precursor indissoluble of metal-salt or insoluble problem, but reaction needed high temperature high pressure process.2, diffusion process.Metal-salt and organic ligand dissolve in a solvent with certain proportion, mixing solutions is put into little glass and is placed in the large bottle that deprotonation solvent is housed, and leave standstill packaged large bottle for some time generation MOF crystal.This method preparation condition is gentle, does not need heating and pressurizing, but crystal growth length consuming time, and reaction precursor at room temperature needs to dissolve.
Except above method, the MOF synthetic method of development in recent years also has electrochemical process, the methods such as microwave and ultrasound.These method crystallizations are quick, narrow diameter distribution and thing mutually easy to control.
By contrast, traditional synthetic method is as low in hydrothermal method and diffusion process have cost, and preparation is simple, crystal purity and the high advantage of quality, but hydrothermal method still needs High Temperature High Pressure, the crystal growth length consuming time of diffusion process.
Therefore, it is simple that those skilled in the art are devoted to a kind of synthesis technique, without the need to High Temperature High Pressure, and the preparation method of crystalline growth velocity metal-organic framework materials easy to control.
Summary of the invention
The object of this invention is to provide a kind of preparation method of metal-organic framework materials, present method synthesis step is simple, and reproducible, without the need to High Temperature High Pressure, the production rate of crystal is easy to control, with low cost, is applicable to large-scale commercial production.
The invention provides a kind of preparation method of metal-organic framework materials, comprise the following steps:
(1) organic carboxyl acid is dissolved in water or alcoholic solution forms organic carboxylic acid solution;
(2) metal oxide powder is added in organic carboxyl acid solution, form metal salt solution;
(3) inorganic alkali solution is added in metal salt solution, form transparent mixing solutions;
(4) mixing solutions generates metallic organic framework crystal through leaving standstill, or adopts solution method film to form metallic organic framework film.
Further, in step (1), the general formula of organic carboxyl acid is R1-COOH, HOOC-R2-COOH or HOOC-COOH, and wherein R1 is H, CH
3, CH
3-CH
2, C
6h
5or C
6h
5-CH
2, R2 is CH
2, CH
2-CH
2or-C
6h
4-.
Further, in step (1) organic carboxyl acid solution the volume ratio of organic carboxyl acid and water or alcohol between 1:1 to 1:9.
Further, in step (2), metal oxide is ZnO, TiO
2or MgO, metal oxide and organic acid reaction, the organic salt of production is soluble in aqueous solvent or alcohol, is insoluble in organic acid.
Further, in step (2), metal oxide is dissolved in the saturated solubility in organic acid soln, is inversely proportional to the volume ratio of organic carboxyl acid in organic acid soln and water or alcohol.
Further, mixing solutions generates metallic organic framework crystal through leaving standstill in step (4), and the quality that the speed of growth and the metal oxide of metallic organic framework crystal grain join organic carboxyl acid solution is directly proportional.
Further, in step (4), mixing solutions generates metallic organic framework crystal through leaving standstill, and the speed of growth of metallic organic framework crystal grain is directly proportional to the concentration of organic carboxyl acid in organic carboxyl acid solution.
Further, in step (4) solution method film be that rotation is smeared, spray ink Printing or silk screen printing.
Compared with prior art, the preparation method of metal-organic framework materials provided by the invention has following beneficial effect:
(1) without the need to high temperature high pressure process, MOF crystal can be formed fast;
(2) Solution method film prepares MOF film;
(3) not only can obtain the MOF crystal settling be of high quality or film, and synthetic method is simple, preparation process good stability, cost is low, is suitable for large-scale commercial production, and application prospect is considerable.
Accompanying drawing explanation
Fig. 1 is the structure iron of MOF material prepared by the preparation method of the metal-organic framework materials of the employing one embodiment of the present of invention using single crystal X-ray diffraction instrument to record;
Fig. 2 is the topology diagram that the MOF material adopting the preparation method of the metal-organic framework materials of one embodiment of the present of invention to prepare is watched along b axle;
Fig. 3 is monocrystalline and the powder X-ray RD figure of the MOF material adopting the preparation method of the metal-organic framework materials of one embodiment of the present of invention to prepare.
Embodiment
With specific embodiment, technological method of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1
The preparation process of metallic organic framework crystal settling is as follows:
Step 1, the volume ratio of configuration formic acid and water is the formic acid solution of 1:1;
Step 2, gets 60mg Zinc oxide powder, adds in the formic acid solution of 1ml, and because formic acid content is high, the reaction product of zinc oxide and formic acid is poorly soluble in formic acid solution;
Step 3, the ammoniacal liquor getting 0.5ml adds in the solution that step 2 formed, and ammoniacal liquor, with formic acid in formic acid solution, violent thermopositive reaction occurs, and the reaction product of zinc oxide and formic acid is dissolved rapidly, the solution of formation clear;
Step 4, the solution room temperature of clear step 3 formed or 5 DEG C of standing a moments, produces the MOF monocrystalline of clear, colorless;
Fig. 1 is the structure iron of the metal-organic framework materials of the preparation that single crystal X-ray diffraction instrument records, and containing 2 Zn atom centers in MOF, Zn1 is by the O Atomic coordinate on 6 formates, and Zn2 is by the O Atomic coordinate of O Atomic coordinate and 4 water moleculess on 2 formates.
Fig. 2 is the topology diagram that metal-organic framework materials is watched along b axle.
Can use the organic carboxyl acid that general formula is R1-COOH, HOOC-R2-COOH or HOOC-COOH, wherein R1 is H, CH
3, CH
3-CH
2, C
6h
5or C
6h
5-CH
2, R2 is CH
2, CH
2-CH
2or-C
6h
4-.Formic acid is used in the present embodiment.
In organic carboxyl acid solution, the volume ratio of organic carboxyl acid and water or alcohol is between 1:1 to 1:9.In the present embodiment, the volume ratio of formic acid and water is 1:1.
Metal oxide can be ZnO, TiO
2or MgO, metal oxide and organic acid reaction, the organic salt of production is soluble in aqueous solvent or alcohol, is insoluble in organic acid.In the present embodiment, metal oxide is ZnO.
Metal oxide is dissolved in the saturated solubility in organic acid soln, is inversely proportional to the volume ratio of organic carboxyl acid in organic acid soln and water or alcohol.
The quality that the speed of growth and the metal oxide of metallic organic framework crystal grain join organic carboxyl acid solution is directly proportional, and is directly proportional to the concentration of organic carboxyl acid in organic carboxyl acid solution.
Embodiment 2
The preparation process of metallic organic framework film is as follows:
Step 1, the volume ratio of configuration formic acid and water is the formic acid solution of 1:9.
Step 2, gets 60mg Zinc oxide powder, adds in the formic acid solution of 1ml, and because formic acid content is low, the reaction product of zinc oxide and formic acid is dissolved in formic acid solution completely.
Step 3, the ammoniacal liquor getting 0.5ml adds in the solution of step 2 formation, and first adularescent precipitation insolubles generates, and last white precipitate dissolves completely, forms the MOF solution of clear.
Step 4, gets MOF solution and drips on clean ito glass, and spin coating also, after solvent flashing, forms MOF film.
Fig. 3 is the XRD figure of the metal-organic framework materials that powder x-ray diffraction records, and the XRD figure of the metal-organic framework materials of simulating with single crystal X-ray diffraction instrument is almost coincide.
In the present embodiment, the volume ratio of formic acid and water is 1:9.
Solution method film is that rotation is smeared, spray ink Printing or silk screen printing.Rotation is adopted to smear film in the present embodiment.
The preparation method of metal-organic framework materials provided by the invention, without the need to high temperature high pressure process, can form MOF crystal fast; Solution method film prepares MOF film; Not only can obtain the MOF crystal settling or film that are of high quality, and synthetic method is simple, preparation process good stability, cost is low, is suitable for large-scale commercial production, and application prospect is considerable.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (9)
1. a preparation method for metal-organic framework materials, is characterized in that, comprises the following steps:
(1) organic carboxyl acid is dissolved in water or alcoholic solution forms organic carboxylic acid solution;
(2) metal oxide powder is added in described organic carboxyl acid solution, form metal salt solution;
(3) inorganic alkali solution is added in described metal salt solution, form transparent mixing solutions;
(4) described mixing solutions generates metallic organic framework crystal through leaving standstill, or adopts solution method film to form metallic organic framework film.
2. the preparation method of metal-organic framework materials as claimed in claim 1, it is characterized in that, described in step (1), the general formula of organic carboxyl acid is R1-COOH, HOOC-R2-COOH or HOOC-COOH, and wherein R1 is H, CH
3, CH
3-CH
2, C
6h
5or C
6h
5-CH
2, R2 is CH
2, CH
2-CH
2or-C
6h
4-.
3. the preparation method of metal-organic framework materials as claimed in claim 1, it is characterized in that, described in the described organic carboxyl acid solution of step (1), the volume ratio of organic carboxyl acid and water or alcohol is between 1:1 to 1:9.
4. the preparation method of metal-organic framework materials as claimed in claim 1, it is characterized in that, described in step (2), metal oxide is ZnO, TiO
2or MgO.
5. the preparation method of metal-organic framework materials as claimed in claim 1, it is characterized in that, described in step (2), metal oxide is dissolved in the saturated solubility in described organic acid soln, is inversely proportional to the volume ratio of organic carboxyl acid described in described organic acid soln and water or alcohol.
6. the preparation method of metal-organic framework materials as claimed in claim 1, it is characterized in that, described in step (3), mineral alkali is NH
3h
2o, NaOH or Ca (OH)
2.
7. the preparation method of metal-organic framework materials as claimed in claim 1, it is characterized in that, mixing solutions described in step (4) generates metallic organic framework crystal through leaving standstill, and the quality that the speed of growth and the described metal oxide of described metallic organic framework crystal grain join described organic carboxyl acid solution is directly proportional.
8. the preparation method of metal-organic framework materials as claimed in claim 1, it is characterized in that, mixing solutions described in step (4) generates metallic organic framework crystal through leaving standstill, and the speed of growth of described metallic organic framework crystal grain is directly proportional to the concentration of organic carboxyl acid in described organic carboxyl acid solution.
9. the preparation method of metal-organic framework materials as claimed in claim 1, is characterized in that, in step (4) solution method film be that rotation is smeared, spray ink Printing or silk screen printing.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106883425A (en) * | 2017-03-08 | 2017-06-23 | 东北大学 | The method that spray-on process prepares unlimited coordination polymer and Metal-organic frame nano flower |
CN114002201A (en) * | 2021-11-09 | 2022-02-01 | 山西聚微天成科技有限公司 | High-sensitivity ion detection device and application thereof |
US11395991B2 (en) * | 2015-09-29 | 2022-07-26 | Ketai (Beijing) Technology Co., Ltd. | Metal-organic framework filter and preparation method thereof |
Citations (3)
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---|---|---|---|---|
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 |
CN101429209A (en) * | 2008-12-11 | 2009-05-13 | 重庆大学 | Method for low-temperature atmosphere-pressure hydrothermal synthesis of stephanoporate metal-organic framework |
CN103333182A (en) * | 2013-06-04 | 2013-10-02 | 中南大学 | Method for preparing MOF-5 |
-
2014
- 2014-11-17 CN CN201410652749.4A patent/CN104478907A/en active Pending
Patent Citations (3)
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 |
CN101429209A (en) * | 2008-12-11 | 2009-05-13 | 重庆大学 | Method for low-temperature atmosphere-pressure hydrothermal synthesis of stephanoporate metal-organic framework |
CN103333182A (en) * | 2013-06-04 | 2013-10-02 | 中南大学 | Method for preparing MOF-5 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11395991B2 (en) * | 2015-09-29 | 2022-07-26 | Ketai (Beijing) Technology Co., Ltd. | Metal-organic framework filter and preparation method thereof |
CN106883425A (en) * | 2017-03-08 | 2017-06-23 | 东北大学 | The method that spray-on process prepares unlimited coordination polymer and Metal-organic frame nano flower |
CN106883425B (en) * | 2017-03-08 | 2019-12-17 | 东北大学 | Method for preparing unlimited coordination polymer and metal organic framework nano flower by spraying method |
CN114002201A (en) * | 2021-11-09 | 2022-02-01 | 山西聚微天成科技有限公司 | High-sensitivity ion detection device and application thereof |
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