CN112808029A - Method for rapidly growing ZIF-8 film on ceramic substrate - Google Patents
Method for rapidly growing ZIF-8 film on ceramic substrate Download PDFInfo
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- CN112808029A CN112808029A CN202011547444.9A CN202011547444A CN112808029A CN 112808029 A CN112808029 A CN 112808029A CN 202011547444 A CN202011547444 A CN 202011547444A CN 112808029 A CN112808029 A CN 112808029A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/35—Use of magnetic or electrical fields
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Abstract
The invention provides a method for rapidly growing a ZIF-8 film on a ceramic substrate, belonging to the technical field of MOF film preparation. The method comprises the following specific steps: (1) graphite or graphite-containing materials are adopted to coat and scratch the surface of the porous substrate, and the graphite layer has the functions of modifying the rough surface of the substrate and increasing the conductivity of the surface of the substrate; (2) dissolving metal salt and an organic ligand in a solvent, uniformly mixing, and standing to obtain a mixed solution; (3) and (3) placing the graphite modified porous substrate obtained in the step (1) into the mixed solution obtained in the step (2), and externally applying constant current to synthesize the metal organic framework film. The preparation method is prepared by an external constant current method, the operation steps are simple and convenient, the synthesis time is short, the investment cost is low, the production efficiency is high, and the prepared MOF membrane has excellent performance in the field of gas separation.
Description
Technical Field
The invention belongs to the technical field of MOF (metal-organic framework) film preparation, and particularly relates to a method for rapidly growing a ZIF-8 film on a ceramic substrate.
Background
In the development of the modern chemical industry, economic benefit and environmental sustainability are important indexes. In chemical production, rectification separated by virtue of boiling point difference is a main separation device at present, but the cost is too high because energy consumption is large and large equipment investment is needed. Especially for important industrial feedstocks such as propylene and propane, separation is more difficult due to the close boiling points of the two.
Membrane separation technology has experienced rapid development and progress since its introduction in the early part of the last century. Because no heat exchange is involved, the method has the advantages of simple operation and energy saving. The metal-organic framework is a crystal having a regular and adjustable pore size composed of metal ions and organic ligands, and has been widely studied as a material for membrane separation. However, the current applications have the following limitations: firstly, the preparation process is complex and high in cost, and most of the preparation of the metal organic framework film at present is on a sheet-shaped substrate; secondly, the water stability is poor; third, long term operational stability of the metal-organic framework film under practical operating conditions. These problems have greatly limited the practical industrial application of metal organic framework materials. The subject group independently develops a method for rapidly preparing a metal organic framework film by using an electric field, the method has simple steps, the required time is far shorter than other common methods, but the substrate used by the method is anodic alumina, and in order to ensure that the substrate has conductivity, a layer of conductive metal needs to be plated on the surface of the substrate by using a magnetron sputtering method, so the cost is extremely high. To extend the application of this method, the problem of expensive substrates must be solved.
Disclosure of Invention
To solve the disadvantages and shortcomings of the prior art, an object of the present invention is to provide a method of rapidly growing a ZIF-8 film on a ceramic substrate.
The purpose of the invention is realized by the following technical scheme.
A method of rapidly growing a ZIF-8 film on a ceramic substrate, comprising the steps of:
(1) coating graphite or graphite-containing material on the surface of the porous substrate;
(2) dissolving metal salt and an organic ligand in a solvent, uniformly mixing, and standing to obtain a mixed solution;
(3) and (3) placing the graphite modified porous substrate obtained in the step (1) into the mixed solution obtained in the step (2), and externally applying constant current to synthesize the metal organic framework film.
Preferably, the graphite coating amount of the surface of the porous substrate in the step (1) is 2-50 g/m2。
Preferably, the porous substrate in step (1) is a ceramic sheet, a ceramic hollow fiber or a ceramic tube.
Preferably, the metal salt in step (2) is zinc acetate dihydrate, the organic ligand is dimethyl imidazole, and the solvent is methanol.
Preferably, the concentration of the metal salt in the mixed solution in the step (2) is 0.01-0.1 mol/L, and the molar ratio of the metal salt to the organic ligand is 0.1-1: 1.
preferably, the standing time in the step (2) is 12-24 hours.
Preferably, the constant current applied in the step (3) is 0.5-2 mA-cm-2The synthesis time is 10-30 minutes.
Preferably, the porous substrate in the step (1) is subjected to ultrasonic treatment for 5-10 min by using deionized water, and is placed in an oven for drying for 12-24 h
The metal organic framework film is prepared by one step by the in-situ electric field method, so that much time can be saved in actual operation, and the operation steps are greatly simplified. The film prepared by the method has no obvious defect on the surface, good contact with the substrate and no obvious crack
Compared with the prior art, the invention has the following advantages:
compared with the traditional hydrothermal method, the metal organic framework film prepared on the ceramic porous substrate by utilizing the in-situ electric field greatly simplifies the operation steps in the actual operation. And the metal organic frame film can grow on the flaky, tubular or hollow fibrous ceramic substrate at normal temperature and pressure, the synthesized thin layer is tightly contacted with the substrate without layering, and the possibility of enlarged production is provided.
Drawings
FIG. 1 is a surface view of a thin layer of the inner surface of a ZIF-8 membrane @ ceramic hollow fiber prepared in example 3.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the embodiments and the protection scope of the present invention are not limited thereto.
Example 1
In the embodiment, the ZIF-8 film is prepared on the porous alumina sheet by one step by using an in-situ electric field method, and the method comprises the following steps:
(1) using 800, 2000 and 5000 meshes of sand paper to sequentially polish commercial porous aluminum oxide sheets (the thickness is 1mm, the diameter is 17.8mm, and the average pore diameter is 100nm), then using deionized water to perform ultrasonic treatment for 5min, and placing the aluminum oxide sheets into an oven to dry for 12 h;
(2) scratching the ceramic hollow fiber obtained in the step (1) by using a stone grinding rod, wherein the coating amount is 20g/m2。
(3) Preparing a precursor solution required by electrodeposition: weighing zinc acetate dihydrate ((CH)3COO)2Zn·2H2O) 1g of the granules was dissolved in 100mL of methanol, 0.8g of dimethylimidazole was added thereto, and stirred at room temperature for half an hour to give a colorless transparent clear solution, which was allowed to stand for 12 hours to give a precursor solution.
(4) In-situ electric field next step synthesis of ZIF8 film: immersing the substrate in the step (2) into precursor liquid for synthesizing ZIF-8 film, and adding 0.7 mA-cm-2The reaction is carried out for 20min at room temperature, and a ZIF-8 film is generated on the surface of the substrate.
Example 2
In the embodiment, the ZIF-8 membrane is prepared on the outer surface of the ceramic hollow fiber by one step by using an in-situ electric field method, and the method comprises the following steps:
(1) using 800, 2000 and 5000 meshes of sand paper to sequentially polish the outer surface of commercial ceramic hollow fibers (the length is 6cm, the outer diameter is 4mm, the inner diameter is 3mm, and the average pore diameter of the outer surface is 3 mu m), then using deionized water to carry out ultrasonic treatment for 5min, and placing the fibers into an oven to dry for 12 h;
(2) scratching the outer surface of the ceramic hollow fiber obtained in the step (1) by using a stone grinding rod, wherein the coating amount is 30g/m2。
(3) Preparing a precursor solution required by electrodeposition: weighing zinc acetate dihydrate ((CH3COO)2Zn·2H2O) 1g of the granules was dissolved in 100mL of methanol, 0.8g of dimethylimidazole was added thereto, and stirred at room temperature for half an hour to give a colorless transparent clear solution, which was allowed to stand for 12 hours to give a precursor solution.
(4) And (3) synthesizing a ZIF-8 film in the next step by using an in-situ electric field: immersing the substrate in the step (2) into precursor liquid for synthesizing ZIF-8 film, and adding 1 mA-cm-2The current is reacted for 20min at room temperature, and a ZIF-8 film is generated on the outer surface of the substrate.
Example 3
In the embodiment, the ZIF-8 membrane is prepared on the inner surface of the ceramic hollow fiber by one step by using an in-situ electric field method, and the method comprises the following steps:
(1) commercial ceramic hollow fibers (6 cm in length, 4mm in outer diameter, 3mm in inner diameter and 100nm in average inner surface pore diameter) are subjected to ultrasonic treatment with deionized water for 5min, and then dried in an oven for 12 h;
(2) scratching the inner surface of the ceramic hollow fiber obtained in the step (1) by using a stone grinding rod, wherein the coating amount is 20g/m2。
(3) Preparing a precursor solution required by electrodeposition: weighing zinc acetate dihydrate ((CH)3COO)2Zn·2H2O) 1g of the granules was dissolved in 100mL of methanol, 0.8g of dimethylimidazole was added thereto, and stirred at room temperature for half an hour to give a colorless transparent clear solution, which was allowed to stand for 12 hours to give a precursor solution.
(4) And (3) synthesizing a ZIF-8 film in the next step by using an in-situ electric field: immersing the substrate in the step (2) into precursor liquid for synthesizing ZIF-8 film, and adding 1 mA-cm-2The current of (2) is reacted for 20min at room temperature, and a ZIF-8 film is generated on the inner surface of the substrate.
And (3) performing scanning electron microscope characterization on the thin layer on the inner surface of the ZIF-8 membrane @ ceramic hollow fiber, wherein the thin layer is flat and has no obvious defects as shown in figure 1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, combinations, modifications, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, combinations, modifications, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A method of rapidly growing a ZIF-8 film on a ceramic substrate, comprising the steps of:
(1) coating graphite or graphite-containing material on the surface of the porous substrate;
(2) dissolving metal salt and an organic ligand in a solvent, uniformly mixing, and standing to obtain a mixed solution;
(3) and (3) placing the graphite modified porous substrate obtained in the step (1) into the mixed solution obtained in the step (2), and externally applying constant current to synthesize the metal organic framework film.
2. The method according to claim 1, wherein the graphite coating amount on the surface of the porous substrate in the step (1) is 2 to 50g/m2。
3. The method of claim 1, wherein the porous substrate in step (1) is a ceramic sheet, a ceramic hollow fiber or a ceramic tube.
4. The method of claim 1, wherein the metal salt in step (2) is zinc acetate dihydrate, the organic ligand is dimethylimidazole, and the solvent is methanol.
5. The method according to claim 1, wherein the concentration of the metal salt in the mixed solution in the step (2) is 0.01 to 0.1mol/L, and the molar ratio of the metal salt to the organic ligand is 0.1 to 1: 1.
6. the method according to claim 1, wherein the standing time in the step (2) is 12 to 24 hours.
7. The method of claim 1, wherein the applied constant current in step (3) is 0.5-2 mA-cm-2The synthesis time is 10-30 minutes.
8. The method according to claim 1, wherein the porous substrate in the step (1) is subjected to ultrasonic treatment with deionized water for 5-10 min, and then is placed in an oven for drying for 12-24 h.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550029A (en) * | 2009-04-30 | 2009-10-07 | 北京科技大学 | A graphite electrode functional ceramic device and its preparation method |
| CN102247764A (en) * | 2011-07-26 | 2011-11-23 | 南京工业大学 | Carbon/graphite/porous matrix composite membrane and preparation method and application thereof |
| CN102784562A (en) * | 2012-08-09 | 2012-11-21 | 大连理工大学 | Method for preparing metal organic framework film |
| CN104415670A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院宁波材料技术与工程研究所 | Metal organic framework membrane and preparation method and application thereof |
| CN104959044A (en) * | 2015-06-30 | 2015-10-07 | 浙江工业大学 | Method for synthesizing metal organic framework film |
| CN105588860A (en) * | 2015-12-13 | 2016-05-18 | 中国科学院福建物质结构研究所 | Transition metal oxide surface heteroepitaxial metal organic framework shell layer and preparation method and application thereof |
| CN105879707A (en) * | 2016-07-03 | 2016-08-24 | 景德镇陶瓷大学 | Reduced-oxidized graphene modified ceramic membrane with efficient ion rejection performance |
| CN107020022A (en) * | 2017-04-26 | 2017-08-08 | 山东工业陶瓷研究设计院有限公司 | A kind of sewage disposal earthenware slab UF membrane film layer and its preparation technology |
| CN107364844A (en) * | 2017-05-31 | 2017-11-21 | 广东工业大学 | A kind of steam reduction graphene oxide conductive polymer composite film and preparation method and application |
| CN107398187A (en) * | 2017-07-26 | 2017-11-28 | 华南理工大学 | It is a kind of to utilize the supper-fast method for preparing metal organic framework film of electric field poling |
| US20180141006A1 (en) * | 2015-05-07 | 2018-05-24 | Forschungszentrum Juelich Gmbh | Carbon-Containing Membrane for Water and Gas Separation |
| CN109731551A (en) * | 2019-02-23 | 2019-05-10 | 华南理工大学 | A kind of metallic organic frame films extract the application of helium in rich-helium type natural gas |
| CN111686587A (en) * | 2020-06-29 | 2020-09-22 | 山东理工大学 | Method for preparing metal organic framework material film on double-layer hollow fiber |
-
2020
- 2020-12-23 CN CN202011547444.9A patent/CN112808029A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550029A (en) * | 2009-04-30 | 2009-10-07 | 北京科技大学 | A graphite electrode functional ceramic device and its preparation method |
| CN102247764A (en) * | 2011-07-26 | 2011-11-23 | 南京工业大学 | Carbon/graphite/porous matrix composite membrane and preparation method and application thereof |
| CN102784562A (en) * | 2012-08-09 | 2012-11-21 | 大连理工大学 | Method for preparing metal organic framework film |
| CN104415670A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院宁波材料技术与工程研究所 | Metal organic framework membrane and preparation method and application thereof |
| US20180141006A1 (en) * | 2015-05-07 | 2018-05-24 | Forschungszentrum Juelich Gmbh | Carbon-Containing Membrane for Water and Gas Separation |
| CN104959044A (en) * | 2015-06-30 | 2015-10-07 | 浙江工业大学 | Method for synthesizing metal organic framework film |
| CN105588860A (en) * | 2015-12-13 | 2016-05-18 | 中国科学院福建物质结构研究所 | Transition metal oxide surface heteroepitaxial metal organic framework shell layer and preparation method and application thereof |
| CN105879707A (en) * | 2016-07-03 | 2016-08-24 | 景德镇陶瓷大学 | Reduced-oxidized graphene modified ceramic membrane with efficient ion rejection performance |
| CN107020022A (en) * | 2017-04-26 | 2017-08-08 | 山东工业陶瓷研究设计院有限公司 | A kind of sewage disposal earthenware slab UF membrane film layer and its preparation technology |
| CN107364844A (en) * | 2017-05-31 | 2017-11-21 | 广东工业大学 | A kind of steam reduction graphene oxide conductive polymer composite film and preparation method and application |
| CN107398187A (en) * | 2017-07-26 | 2017-11-28 | 华南理工大学 | It is a kind of to utilize the supper-fast method for preparing metal organic framework film of electric field poling |
| CN109731551A (en) * | 2019-02-23 | 2019-05-10 | 华南理工大学 | A kind of metallic organic frame films extract the application of helium in rich-helium type natural gas |
| CN111686587A (en) * | 2020-06-29 | 2020-09-22 | 山东理工大学 | Method for preparing metal organic framework material film on double-layer hollow fiber |
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