CN111672341A - Method for preparing bimetallic MOF (Metal organic framework) membrane by utilizing self-transformation of hydroxyl bimetallic salt and pervaporation separation application - Google Patents
Method for preparing bimetallic MOF (Metal organic framework) membrane by utilizing self-transformation of hydroxyl bimetallic salt and pervaporation separation application Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
Abstract
The invention provides a method for preparing a bimetallic MOF (Metal-organic framework) membrane by utilizing self-transformation of hydroxyl bimetallic salt and application of pervaporation separation, which comprises the steps of introducing a ZnO nano active layer on the surface of a porous carrier, and then carrying out in-situ treatment on the introduced ZnO nano active layer by using a cobalt nitrate solution to obtain a zinc/cobalt hydroxyl bimetallic salt layer serving as a connecting layer for connecting a membrane layer and the carrier and a growth point for growth of the MOF membrane layer; finally, the carrier is placed in a film forming solution without a metal source, and a continuous and complete zinc/cobalt bimetallic MOF film layer is obtained through solvent thermal conversion growth. The preparation method effectively solves the problem of difficulty in the existing preparation of the bimetallic MOF film, and has the characteristics of simplicity, convenience, high efficiency and easiness in large-scale preparation. The membrane shows excellent separation performance and good operation stability to the separation performance of the methanol/methyl tert-butyl ether azeotrope, and has potential practical application value.
Description
Technical Field
The invention provides a method for preparing a bimetallic MOF (Metal organic framework) membrane by utilizing self-transformation of hydroxyl bimetallic salt and a pervaporation separation technology, and opens up a new way for preparing a high-performance bimetallic MOF membrane.
Background
In recent years, due to the great increase of energy consumption and the enhancement of environmental awareness of people, compared with separation technologies such as evaporation, rectification and the like with high energy consumption and high pollution, a membrane separation technology is paid attention to by scientific researchers due to the advantages of energy conservation, high efficiency, simplicity in operation, low energy consumption, environmental friendliness and the like. Membrane separation performance is generally limited by the upper robertson limit, and separation performance depends on the physical and chemical properties of the membrane material, and thus, it is urgently required to find a new membrane material with high performance.
Metal Organic Frameworks (MOFs) are porous crystalline materials formed by coordination and combination of metal ions or ion clusters and organic ligands, have the advantages of high specific surface area, designability of framework structure composition, good post-modification property, pore size adjustability, high stability and the like, and have wide attention on potential applications in the aspects of separation, catalysis, drug transportation, electronic sensing and the like. The bimetallic MOFs refers to that a single MOFs crystal skeleton structure simultaneously contains two metal ions, although the research on the bimetallic MOFs is still in a starting stage, the bimetallic MOFs has a more excellent effect in some application aspects compared with the traditional single-metal MOFs, for example, in the field of gas adsorption and storage, the stability and the affinity to a target gas can be greatly improved by introducing the second metal ions into the MOFs crystal; generally, due to the rotation of the organic ligand, the channel of the MOFs may generate a "gate opening effect" to change the channel size, and the channel size of the MOFs may be precisely adjusted and controlled by introducing a second metal ion. For example, Jeong et al replace some Zn ions in ZIF-8 with Co ions, the crystal structure is not damaged, and the Co-N bond is more rigid than the Zn-N bond, thus inhibiting the ligand from rotating and reducing the effective pore diameter of the crystal; in addition, the addition of Co enhances the intercrystalline structure of the film and improves the separation performance of the film [ Hillman F, Zimmerman J M, Paek S M, ethyl. Rapid microwave-induced synthesis of hybrid-ionic-membranes metals and hybrid linkers [ J ]. Journal of materials chemistry A,2017,5(13): 6090-.
At present, the preparation of the bimetallic MOFs mostly adopts a one-pot method or a post-synthesis ion exchange method, wherein the one-pot method means that the MOFs synthetic solution contains two metal ions at the same time, but the two metal ions are difficult to ensure to react at the same time, so that the formation of physically mixed single-metal MOFs is avoided. For example, Serre et al used a one-pot process with the addition of Fe3+And Cr3+To produce bimetallic MIL-53(Cr/Fe) material, but due to Cr3+Compared with Fe3+More inert, cannot ensure that two metal ions react simultaneously, and inert Fe is selected0To replace Fe3+Can ensure that two metal ions react simultaneously, namely the introduction of two metals is controlled by controlling the reactivity of the metal ions [ Nouar F, Devic T, Chevreau H, et al].Chemical Communications,2012,48(82):10237-10239]. Post-synthesis ion exchange refers to the process of immersing a single metal MOFs in a synthetic solution containing another metal ion for several days to achieve the purpose of ion exchange, but the process is time-consuming and energy-consuming. Therefore, it is of great significance to develop a simple and efficient synthesis method for preparing the bimetallic MOFs film, but still has great challenges.
Hydroxy bimetallic salts (HDSs) are called anion-exchanging layered compounds, which consist of cationic sheets and interlayer anions and are prepared by reacting a divalent metal oxide with another divalent metal cation. HDSs have high ion exchange rates, and HDSs are used as intermediates to rapidly prepare MOFs, such as HKUST-1, ZIF-8, Cu-BDC and IRMOF-3, which are synthesized by Zhao et al at room temperature, and the versatility of the synthesis method is demonstrated [ ZHao J, Nunn W T, Lemaire P C, et al. Zhang et al also rapidly prepared hierarchical pore containing ZIF-8, ZIF-61 and ZIF-90[ Zhang H, Huo J, Yang H, et al. Green and Rapid preparation of hierarchical pore with HDSs ] 2019,7(3):1022-1029 ]. Although the synthesis of MOFs by taking HDSs as intermediates is very advantageous, the MOFs crystals synthesized by using HDSs are all monometallic MOFs, and the subsequent application is limited because no report of preparing MOFs films by means of HDSs is provided. In view of the fact that HDSs can promote the synthesis of ultrafast MOFs and have two metal ions at the same time, the invention provides a technology for preparing bimetallic MOFs membranes by providing metal salts for intermediates by using HDSs.
Disclosure of Invention
Aiming at the problem of difficulty in preparation of the existing bimetallic MOF film, the invention provides a method for preparing a zinc/cobalt bimetallic MOF film by self-transformation by using hydroxyl bimetallic salt (HDS) as an activity induction intermediate.
The invention has the following inventive concept: firstly, introducing a ZnO nano active layer on the surface of a porous carrier, namely introducing a ZnO nano particle layer by a sol-gel pulling method or growing a ZnO nano array layer by a hydrothermal synthesis method; then reacting with cobalt nitrate aqueous solution to obtain a zinc/cobalt hydroxyl double metal salt layer (HDS layer); and finally, placing the carrier introduced with the HDS layer in an organic ligand synthetic solution without a metal source, and forming a continuous and complete zinc/cobalt bimetallic MOFs film layer through solvothermal growth. The synthesis method can effectively solve the problem of preparation of the existing bimetallic MOF film layer, is simple and efficient, is green and pollution-free, and has good novelty and great application prospect.
The technical scheme of the invention is as follows:
a method for preparing zinc/cobalt bimetallic MOFs membrane by utilizing self-transformation of hydroxyl bimetallic salt is disclosed, wherein the zinc/cobalt bimetallic MOFs is a bimetallic MOF structure formed by coordination of taking zinc and cobalt as metal sources and taking dimethyl imidazole or benzimidazole as organic ligands, and a carrier is a porous ceramic tube or ceramic wafer with the average pore diameter of 200 nm-2 mu m, and the method comprises the following specific steps:
(1) introducing ZnO nanoparticles or ZnO nano-array active layer on the surface of a carrier
Mixing ethylene glycol monomethyl ether and zinc acetate according to the weight ratio of (15-30): 1, stirring the mixture for 20-60 min in water bath at 70 ℃, and then slowly dropwise adding a small amount of ethanolamine, wherein the molar ratio of the ethanolamine to the zinc acetate is 2: 1, stirring at room temperature for 12-24 hours to obtain zinc sol; introducing a zinc sol layer to the surface of the carrier by means of lifting or spin coating, and roasting at 400-500 ℃ for 200min to obtain a ZnO nanoparticle active layer;
on the basis of the ZnO nano particle active layer, putting the ZnO nano particle active layer into hexamethylenetetramine, zinc nitrate hexahydrate and a mixture of water in a molar ratio of 1: 1: and reacting for 3-6 h at 100 ℃ in 500 ZnO nano-array synthetic solution to obtain the ZnO nano-array active layer.
(2) Preparation of hydroxyl double metal salt layer on carrier
Placing the carrier introduced with the ZnO nano particles or the ZnO nano array active layer into a cobalt nitrate solution, and reacting for 2-24 hours at 25-100 ℃ to obtain a zinc/cobalt hydroxyl double-metal salt layer; the cobalt nitrate solution in the step (2) is composed of hexahydrate and a cobalt nitrate aqueous solution, wherein the molar ratio of cobalt nitrate hexahydrate to water is (1-5): 500.
(3) and (3) placing the carrier introduced with the zinc/cobalt hydroxyl double-metal salt layer into the zinc/cobalt double-metal MOFs membrane layer synthetic solution, and carrying out high-temperature reaction in a polytetrafluoroethylene stainless steel reaction kettle to obtain the zinc/cobalt double-metal MOFs membrane layer.
Further, the zinc/cobalt bimetallic MOFs membrane layer prepared in the step (3) refers to a zinc/cobalt bimetallic ZIF membrane layer, namely a bimetallic ZIF-8 or ZIF-67 membrane layer which takes zinc ions and cobalt ions as metal centers at the same time and dimethyl imidazole as an organic ligand; or a bimetallic ZIF-7 or ZIF-9 film layer which is composed of zinc ions and cobalt ions as metal centers and benzimidazole as organic ligands.
When the bimetallic ZIF-8 or ZIF-67 film layer is prepared in the step (3), the molar ratio of the dimethyl imidazole, the sodium formate and the water in the synthetic liquid is 10: 1: (800-1200), the reaction temperature is 100-150 ℃, and the reaction time is 5-12 h; when the bimetallic ZIF-7 or ZIF-9 film layer is prepared, the molar ratio of benzimidazole, sodium formate, water and DMF in the synthetic liquid is 10: 1: (250-350): (150-250) the reaction temperature is 100-150 ℃, and the reaction time is 12-24 h.
The method also comprises the following pretreatment steps: selecting a porous ceramic tube or ceramic plate with the average pore diameter of 200 nm-2 mu m as a carrier, respectively ultrasonically cleaning by deionized water and absolute ethyl alcohol before use, and drying in a vacuum oven.
The invention also aims to protect the application of the zinc/cobalt bimetallic MOFs membrane prepared by the method in pervaporation separation. The specific application method comprises the following steps: bimetallic zinc/cobaltThe MOFs membrane is placed in a pervaporation device to separate a mixture, wherein the mixture is preferably methanol/methyl tert-butyl ether, the pressure for measuring the permeation is 0.1MPa, the temperature is 50 ℃, the flow rate is 500mL/h, a cold trap is used for collecting products for measuring the permeation, the products are analyzed by gas chromatography, and the permeation flux is up to 1.5 kg-m-2·h-1Above, the separation factor of methanol/methyl t-butyl ether exceeds 6000.
The invention has the beneficial effects that:
the method for preparing the zinc/cobalt bimetallic MOFs film by utilizing the self-transformation of the hydroxyl bimetallic salt solves the preparation problem of the existing bimetallic MOFs film, has the advantages of simplicity, convenience, high efficiency, easiness in synthesis and the like, has certain universality for the preparation of other kinds of bimetallic MOFs films, and has wide application prospect and potential.
Drawings
FIG. 1a is a SEM image of the surface of the ZnO nano-array prepared in example 2.
FIG. 1b is a SEM image of the cross section of the ZnO nano-array prepared in example 2.
Fig. 2a is a SEM image of the surface of the zinc-cobalt hydroxy double metal salt layer prepared in example 2.
Fig. 2b is a cross-sectional SEM image of the zinc-cobalt hydroxy double metal salt layer prepared in example 2.
FIG. 3a is a SEM image of the surface of a layer of a bimetallic ZIF-8-67 film prepared in example 2.
FIG. 3b is a SEM image of a cross-section of a dual metal ZIF-8-67 film prepared in example 2.
FIG. 4a is a SEM image of the surface of a bimetallic ZIF-7-9 film prepared in example 3.
FIG. 4b is a SEM image of a cross-section of a dual metal ZIF-7-9 film prepared in example 3.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
Example 1
(1) An alumina porous ceramic tube with the average pore diameter of 200nm is selected as a carrier, ultrasonic cleaning is respectively carried out for 20min by deionized water and absolute ethyl alcohol before use, and drying is carried out for 2h in a vacuum oven at 80 ℃.
(2) 8.2624g of zinc acetate and 50mL of ethylene glycol monomethyl ether are added into a 100mL flat-bottomed flask, stirred in a water bath at 70 ℃ for 30min, then 4.6mL of ethanolamine is added, and stirred at room temperature for 24h to prepare a uniform zinc sol solution with the zinc mass fraction of 30%. And (2) then, pulling the zinc sol solution on the porous ceramic tube carrier in the step (1) for 3 times, placing the porous ceramic tube carrier in a 100 ℃ oven for drying for 1h after pulling each time, and finally calcining the porous ceramic tube carrier in a muffle furnace at 400 ℃ for 200min to obtain the ZnO nanoparticle active layer.
(3) And (3) vertically suspending the carrier with the ZnO nano particle active layer introduced in the step (2) in a cobalt nitrate aqueous solution, wherein the molar ratio of the carrier is cobalt nitrate hexahydrate: water 1: 100, reacting at room temperature for 12h to obtain a zinc/cobalt hydroxyl double-metal salt layer vertical to the carrier.
(4) And (3) vertically suspending the carrier introduced with the zinc-cobalt hydroxyl double-metal salt layer in the step (3) in a synthetic solution of the double-metal MOFs membrane, wherein the synthetic solution comprises dimethyl imidazole in a molar ratio: sodium formate: water 10: 1: 1100, reacting for 6 hours in a stainless steel reaction kettle made of polytetrafluoroethylene at the temperature of 100 ℃, taking out the ceramic tube after the reaction is finished, slowly washing the surface of the membrane layer by using absolute ethyl alcohol, and then drying in a vacuum oven at the temperature of 40 ℃ for 24 hours to obtain a compact and complete bimetal ZIF-8 or ZIF-67 membrane layer.
Example 2
In this example, the step (1) and the step (2) are the same as in example 1.
(3) Dissolving 2.38g of hexahydrate and zinc nitrate in 40mL of deionized water, stirring until the hexahydric and the zinc nitrate are dissolved, dissolving 1.12g of hexamethylenetetramine in 40mL of deionized water, stirring until the hexahydric and the zinc nitrate are dissolved, mixing and stirring the two for 20min, vertically suspending the carrier with the ZnO nanoparticle active layer introduced in the step (2) in the solution, and reacting in a stainless steel reaction kettle of polytetrafluoroethylene at the temperature of 100 ℃ for 6h to obtain the ZnO nano array active layer.
(4) And (3) vertically suspending the carrier with the ZnO nano array active layer introduced in the step (3) in a cobalt nitrate aqueous solution, wherein the molar ratio of the carrier is cobalt nitrate hexahydrate: water 1: 100, reacting at room temperature for 24h to obtain a zinc-cobalt hydroxyl double-metal salt layer vertical to the carrier.
(5) And (3) vertically suspending the carrier introduced with the zinc/cobalt hydroxyl double-metal salt layer in the step (4) in a synthetic solution of the double-metal MOFs membrane, wherein the synthetic solution comprises dimethyl imidazole in a molar ratio: sodium formate: water 10: 1: 1100, reacting for 12 hours in a stainless steel reaction kettle made of polytetrafluoroethylene at the temperature of 100 ℃, taking out the ceramic tube after the reaction is finished, slowly washing the surface of the membrane layer by using absolute ethyl alcohol, and then drying for 24 hours in a vacuum oven at the temperature of 40 ℃ to obtain a compact and complete bimetal ZIF-8 or ZIF-67 membrane layer.
Example 3
In this example, the step (1) and the step (2) are the same as in example 1.
(3) And (3) vertically suspending the carrier with the ZnO nano particle active layer introduced in the step (2) in a cobalt nitrate aqueous solution, wherein the molar ratio of the carrier is cobalt nitrate hexahydrate: water 1: 100, reacting at room temperature for 10h to obtain a zinc/cobalt hydroxyl double-metal salt layer vertical to the carrier.
(4) And (3) vertically suspending the carrier introduced with the zinc-cobalt hydroxyl double-metal salt layer in the step (3) in a synthetic solution of the double-metal MOFs membrane, wherein the molar ratio of each component in the synthetic solution is benzimidazole: sodium formate: water: DMF ═ 10: 1: 300: 200, the reaction temperature is 120 ℃, the reaction time is 24 hours, the ceramic tube is taken out after the reaction is finished, the surface of the membrane layer is slowly washed by absolute ethyl alcohol, and then the membrane layer is placed in a vacuum oven at 40 ℃ for drying for 24 hours, so that a compact and complete bimetal ZIF-7 or ZIF-9 membrane layer is obtained.
The bimetallic ZIF-8 or ZIF-67 membrane layer of example 2 prepared in accordance with the present invention was placed in a pervaporation unit to separate a methanol/methyl tert-butyl ether mixture wherein the methanol mass fraction was 15%, the azeotropic composition of methanol and methyl tert-butyl ether (methanol mass fraction was 14.3%), the pressure measured at the permeate was 0.1MPa, temperature 50 ℃, flow rate 500mL/h, the permeate was collected using a cold trap and analyzed using gas chromatography: the permeation flux was about 1.9 kg-m-2·h-1The separation factor exceeded 6500.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (7)
1. A method for preparing a zinc/cobalt bimetallic MOF membrane by utilizing self-transformation of hydroxyl bimetallic salt is characterized by comprising the following steps:
(1) introducing ZnO nanoparticles or ZnO nano-array active layer on the surface of a carrier
Mixing ethylene glycol monomethyl ether and zinc acetate according to the weight ratio of (15-30): 1, stirring the mixture for 20-60 min in water bath at 70 ℃, and then slowly dropwise adding a small amount of ethanolamine, wherein the molar ratio of the ethanolamine to the zinc acetate is 2: 1, stirring at room temperature for 12-24 hours to obtain zinc sol; introducing a zinc sol layer to the surface of the carrier by means of lifting or spin coating, and roasting at 400-500 ℃ for 200min to obtain a ZnO nanoparticle active layer;
on the basis of the ZnO nano particle active layer, putting the ZnO nano particle active layer into hexamethylenetetramine, zinc nitrate hexahydrate and a mixture of water in a molar ratio of 1: 1: reacting for 3-6 h at 100 ℃ in 500 ZnO nano-array synthetic solution to obtain a ZnO nano-array active layer;
(2) preparation of hydroxyl double metal salt layer on carrier
Placing the carrier introduced with the ZnO nano particles or the ZnO nano array active layer into a cobalt nitrate solution, and reacting for 2-24 hours at 25-100 ℃ to obtain a zinc/cobalt hydroxyl double-metal salt layer; the cobalt nitrate solution in the step (2) is composed of hexahydrate and a cobalt nitrate aqueous solution, wherein the molar ratio of cobalt nitrate hexahydrate to water is (1-5): 500, a step of;
(3) and (3) placing the carrier introduced with the zinc/cobalt hydroxyl double-metal salt layer into the zinc/cobalt double-metal MOFs membrane layer synthetic solution, and carrying out high-temperature reaction in a polytetrafluoroethylene stainless steel reaction kettle to obtain the zinc/cobalt double-metal MOFs membrane layer.
2. The method according to claim 1, wherein the zinc/cobalt bimetallic MOFs membrane layer prepared in the step (3) is a bimetallic ZIF-8 or ZIF-67 membrane layer which is composed of zinc ions and cobalt ions which are simultaneously used as metal centers and dimethyl imidazole which is used as an organic ligand; or a bimetallic ZIF-7 or ZIF-9 film layer which is composed of zinc ions and cobalt ions as metal centers and benzimidazole as organic ligands.
3. The method as claimed in claim 1, wherein in the step (3), when the bimetallic ZIF-8 or ZIF-67 membrane layer is prepared, the molar ratio of the dimethylimidazole, the sodium formate and the water in the synthetic solution is 10: 1: (800-1200), the reaction temperature is 100-150 ℃, and the reaction time is 5-12 h; when the bimetallic ZIF-7 or ZIF-9 film layer is prepared, the molar ratio of benzimidazole, sodium formate, water and DMF in the synthetic liquid is 10: 1: (250-350): (150-250) the reaction temperature is 100-150 ℃, and the reaction time is 12-24 h.
4. The method of claim 1, further comprising the step of pre-processing: selecting a porous ceramic tube or ceramic plate with the average pore diameter of 200 nm-2 mu m as a carrier, respectively ultrasonically cleaning by deionized water and absolute ethyl alcohol before use, and drying in a vacuum oven.
5. Use of a zinc/cobalt bimetallic MOF membrane prepared by the method of claim 1 for pervaporation separation.
6. The use according to claim 5, wherein the zinc/cobalt bimetallic MOFs membrane is placed in a pervaporation unit to separate the mixture at a pressure of 0.1MPa for permeation measurement and at a temperature of 50 ℃ and at a flow rate of 500mL/h, and the products of permeation measurement are collected by a cold trap and analyzed by gas chromatography.
7. Use according to claim 6, wherein the mixture is methanol/methyl tert-butyl ether.
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| CN115350591A (en) * | 2022-05-03 | 2022-11-18 | 北京工业大学 | Method for preparing metal organic framework pervaporation composite membrane by hydroxyl salt induction |
| CN115445452A (en) * | 2022-09-05 | 2022-12-09 | 南京工业大学 | Oriented ZIF film material and preparation method and application thereof |
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| CN112657350A (en) * | 2020-12-01 | 2021-04-16 | 大连理工大学 | Method for preparing MOF @ MOF hybrid membrane by utilizing two-dimensional nanosheet membrane induced heteroepitaxial growth method |
| CN112657350B (en) * | 2020-12-01 | 2022-06-21 | 大连理工大学 | Method for preparing MOF @ MOF hybrid membrane by utilizing two-dimensional nanosheet membrane induced heteroepitaxial growth method |
| CN112642433A (en) * | 2020-12-29 | 2021-04-13 | 西安交通大学 | Preparation method of two-dimensional flaky porous composite oxide and application of two-dimensional flaky porous composite oxide in control of chlorine-containing volatile organic pollutants |
| CN113828169A (en) * | 2021-10-20 | 2021-12-24 | 嘉兴哲夫埃特环保科技有限公司 | polycoFs/bimetal MOFs composite membrane and preparation method thereof |
| CN113828169B (en) * | 2021-10-20 | 2023-10-20 | 苏州清李新材料科技有限公司 | PolyCOFs/bimetal MOFs composite film and preparation method thereof |
| CN115350591A (en) * | 2022-05-03 | 2022-11-18 | 北京工业大学 | Method for preparing metal organic framework pervaporation composite membrane by hydroxyl salt induction |
| CN115445452A (en) * | 2022-09-05 | 2022-12-09 | 南京工业大学 | Oriented ZIF film material and preparation method and application thereof |
| CN115445452B (en) * | 2022-09-05 | 2023-10-27 | 南京工业大学 | Oriented ZIF (zinc-based film) material and preparation method and application thereof |
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Application publication date: 20200918 |