CN110841715A - Synthesis method of MIL-68(In) MOFs hollow rod - Google Patents
Synthesis method of MIL-68(In) MOFs hollow rod Download PDFInfo
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- CN110841715A CN110841715A CN201911139954.XA CN201911139954A CN110841715A CN 110841715 A CN110841715 A CN 110841715A CN 201911139954 A CN201911139954 A CN 201911139954A CN 110841715 A CN110841715 A CN 110841715A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 44
- 239000013216 MIL-68 Substances 0.000 title claims abstract description 38
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 8
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 8
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 8
- 229940033123 tannic acid Drugs 0.000 claims abstract description 8
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 8
- 229920002258 tannic acid Polymers 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- ZYYDOSLSINDXIQ-UHFFFAOYSA-N O.O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound O.O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZYYDOSLSINDXIQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000005530 etching Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000003486 chemical etching Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The synthesis method of the MIL-68(In) MOFs hollow rod comprises the following steps: dissolving indium nitrate tetrahydrate and terephthalic acid In an organic solvent, heating the obtained mixture In a reaction kettle for a period of time, centrifugally collecting a product, and washing to obtain an MIL-68(In) MOFs solid rod; adding the MIL-68(In) MOFs solid rod into a water solution containing tannic acid, uniformly stirring, heating the obtained mixed solution In a reaction kettle for a period of time, centrifugally collecting a product, and washing to obtain the MIL-68(In) MOFs hollow rod. According to the synthesis method of the MIL-68(In) MOFs hollow rod, tannic acid is introduced as an etching agent, the MIL-68(In) MOFs hollow rod is synthesized by a chemical etching method, the process is simple, and the cost is low; the MIL-68(In) MOFs hollow rod prepared by the method has uniform size and appearance and larger specific surface area, so that the utilization rate of the rod In catalytic chemical reaction is further improved.
Description
Technical Field
The invention relates to preparation of metal-organic framework Materials (MOFs), In particular to a synthesis method of a metal-organic framework material (MIL-68 (In)) hollow rod.
Background
Metal-organic frameworks (MOFs) are a new class of organic-inorganic hybrid materials developed over a decade or so, constructed from organic ligands and inorganic metal units, and generally have diverse topological structures and unique physicochemical properties. How to further increase the specific surface area of the MOFs and further improve the utilization rate of the MOFs in catalytic chemical reactions is a hot spot and a difficult point of current research.
Disclosure of Invention
The invention realizes the synthesis of the MIL-68(In) MOFs hollow rod by the etching of tannic acid on the basis of synthesizing the MIL-68(In) MOFs solid rod, and the synthesis method comprises the following specific steps:
the synthesis method of the MIL-68(In) MOFs hollow rod comprises the following steps:
s1: dissolving indium nitrate tetrahydrate and terephthalic acid In an organic solvent, heating the obtained mixture In a reaction kettle for a period of time, centrifugally collecting a product, and washing to obtain an MIL-68(In) MOFs solid rod;
s2: adding the MIL-68(In) MOFs solid rod into a water solution containing tannic acid, uniformly stirring, heating the obtained mixed solution In a reaction kettle for a period of time, centrifugally collecting a product, and washing to obtain the MIL-68(In) MOFs hollow rod.
Further, the organic solvent is N, N-dimethylformamide.
Further, in the step S1, the heating temperature in the reaction kettle is 100 ℃, and the heating time is 6 hours.
Further, in the step S2, the heating temperature in the reaction kettle is 150 ℃ and the heating time is 1 h.
The invention also provides the MIL-68(In) MOFs hollow rod prepared by the synthesis method.
Compared with the prior art, the invention has the beneficial effects that:
according to the synthesis method of the MIL-68(In) MOFs hollow rod, tannic acid is introduced as an etching agent, the MIL-68(In) MOFs hollow rod is synthesized by a chemical etching method, the process is simple, and the cost is low; the MIL-68(In) MOFs hollow rod prepared by the method has uniform size and appearance and larger specific surface area, so that the utilization rate of the rod In catalytic chemical reaction is further improved.
Drawings
FIG. 1 is an XRD of a precursor prepared according to an embodiment of the present invention;
FIG. 2 is a scanning electron micrograph of a precursor prepared according to an embodiment of the present invention;
FIG. 3 is a transmission electron micrograph of a precursor prepared according to an embodiment of the present invention;
FIG. 4 is an X-ray powder diffraction pattern of MIL-68(In) MOFs hollow rods prepared In accordance with an embodiment of the present invention;
FIG. 5 is a scanning electron microscope image of MIL-68(In) MOFs hollow rods prepared In accordance with an embodiment of the present invention;
FIG. 6 is a transmission electron microscope image of MIL-68(In) MOFs hollow rods prepared In the examples of the present invention.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples
The synthesis method of the MIL-68(In) MOFs hollow rod comprises the following steps:
(1) synthesis of MIL-68(In) MOFs solid rods
Adding 0.2mmol of indium nitrate tetrahydrate and 0.18mmol of terephthalic acid into 10mL of N, N-dimethylformamide solution, heating the mixture In a 25mL reaction kettle to 100 ℃, reacting for 6h, centrifuging, collecting the product, and washing with industrial alcohol for 4 times to obtain the MIL-68(In) MOFs solid rod with uniform size and appearance. FIG. 1 shows XRD of the precursor under the above experimental conditions, and from the XRD pattern, the obtained product is MIL-68(In) MOFs. FIG. 2 shows the scanning electron microscope image of the precursor, and it can be seen from FIG. 2 that the obtained product is a rod-like micron material, and the size of the particles is relatively uniform, and the length is about 3 μm. FIG. 3 is a transmission electron microscope image of the precursor, and it can be seen from FIG. 3 that the obtained product is a rod-like micron material, the size of the particles is relatively uniform, and the interior of the particles is a solid structure.
(2) Synthesis of MIL-68(In) MOFs hollow bars
Adding 10mg of the product into an aqueous solution containing 10mg of tannic acid, uniformly stirring, heating the obtained mixed solution to 150 ℃ In a 25mL reaction kettle, reacting for 1h, centrifugally collecting the product, and washing with industrial alcohol for 4 times to obtain the MIL-68(In) MOFs hollow rod with uniform size and shape. FIG. 4 shows XRD of the samples after tannic acid etching, with the XRD pattern showing that the resulting product is still MIL-68(In) MOFs. Fig. 5 is a scanning electron microscope image of the sample after etching, and it can be seen from fig. 5 that the obtained product is a rod-shaped micron material with a hollow structure, the size of the particles is relatively uniform, and the rod-shaped material is in the hollow structure. Fig. 6 shows a Transmission Electron Micrograph (TEM) of the etched sample, and it can be seen from fig. 6 that the resulting product has a hollow rod-like structure.
Claims (5)
- A synthesis method of MIL-68(In) MOFs hollow rods is characterized by comprising the following steps:s1: dissolving indium nitrate tetrahydrate and terephthalic acid In an organic solvent, heating the obtained mixture In a reaction kettle for a period of time, centrifugally collecting a product, and washing to obtain an MIL-68(In) MOFs solid rod;s2: adding the MIL-68(In) MOFs solid rod into a water solution containing tannic acid, uniformly stirring, heating the obtained mixed solution In a reaction kettle for a period of time, centrifugally collecting a product, and washing to obtain the MIL-68(In) MOFs hollow rod.
- 2. The method for synthesizing MIL-68(In) MOFs hollow rods according to claim 1, wherein the organic solvent is N, N-dimethylformamide.
- 3. The method for synthesizing MIL-68(In) MOFs hollow rods according to claim 1, wherein the heating temperature In the reaction kettle is 100 ℃ and the heating time is 6h In step S1.
- 4. The method for synthesizing MIL-68(In) MOFs hollow rods according to claim 1, wherein the heating temperature In the reaction kettle is 150 ℃ and the heating time is 1h In step S2.
- 5. Hollow rods of MIL-68(In) MOFs prepared by the synthesis method of any of the preceding claims.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911139954.XA CN110841715A (en) | 2019-11-20 | 2019-11-20 | Synthesis method of MIL-68(In) MOFs hollow rod |
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| CN201911139954.XA CN110841715A (en) | 2019-11-20 | 2019-11-20 | Synthesis method of MIL-68(In) MOFs hollow rod |
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| CN110841715A true CN110841715A (en) | 2020-02-28 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11167274B2 (en) * | 2019-05-16 | 2021-11-09 | Soochow University | In—NH2/g-C3N4 nanocomposite with visible-light photocatalytic activity and preparation and application thereof |
| CN113813938A (en) * | 2021-10-22 | 2021-12-21 | 福州大学 | Rod-shaped modified iron-nickel organic framework composite adsorbent |
| CN114345418A (en) * | 2021-12-27 | 2022-04-15 | 东北大学 | Hollow tubular MIL-68(In)/In2S3/ZnIn2S4Preparation method and application of photocatalyst |
| CN114464786A (en) * | 2022-01-09 | 2022-05-10 | 福建师范大学 | Electrode material of potassium ion battery and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876776A (en) * | 2019-02-02 | 2019-06-14 | 北京建筑大学 | Indium base MOF micro-nano powder and its room temperature preparation method and application |
-
2019
- 2019-11-20 CN CN201911139954.XA patent/CN110841715A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876776A (en) * | 2019-02-02 | 2019-06-14 | 北京建筑大学 | Indium base MOF micro-nano powder and its room temperature preparation method and application |
Non-Patent Citations (2)
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| HUAZHEN SUN ET AL.: ""Hydrophilic hollow zeolitic imidazolate framework-8 modified ultrafiltration membranes with significantly enhanced water separation properties"", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| MING HU ET AL.: ""Void Engineering in Metal–Organic Frameworks via Synergistic Etching and Surface Functionalization"", 《ADVANCED FUNCTIONAL MATERIALS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11167274B2 (en) * | 2019-05-16 | 2021-11-09 | Soochow University | In—NH2/g-C3N4 nanocomposite with visible-light photocatalytic activity and preparation and application thereof |
| CN113813938A (en) * | 2021-10-22 | 2021-12-21 | 福州大学 | Rod-shaped modified iron-nickel organic framework composite adsorbent |
| CN114345418A (en) * | 2021-12-27 | 2022-04-15 | 东北大学 | Hollow tubular MIL-68(In)/In2S3/ZnIn2S4Preparation method and application of photocatalyst |
| CN114464786A (en) * | 2022-01-09 | 2022-05-10 | 福建师范大学 | Electrode material of potassium ion battery and preparation method and application thereof |
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