CN107158964B - Composite membrane material based on metal organic framework nanosheets and graphene oxide, preparation method and application in gas separation - Google Patents
Composite membrane material based on metal organic framework nanosheets and graphene oxide, preparation method and application in gas separation Download PDFInfo
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Abstract
A composite membrane material based on metal organic framework nanosheets and graphene oxide and application thereof in gas separation belong to the technical field of membrane materials and separation thereof. Firstly, preparing a metal oxide nanosheet at room temperature, paving the metal oxide nanosheet and graphene oxide dispersion liquid into a composite membrane material by a layer-by-layer method, wherein graphene oxide is used as a main body of the membrane, and the metal oxide nanosheet is doped in the graphene oxide. And reacting the obtained composite membrane material with an organic ligand to convert the composite membrane material into the graphene oxide composite membrane material doped with the metal organic framework nanosheets. By adopting the strategy, the metal organic framework material with uniform pore channels is introduced into the membrane material while the ultrathin thickness is successfully maintained, so that the separation selectivity is improved by 6 times compared with that of a pure graphene oxide membrane, and the improvement is obvious compared with that of a membrane material obtained by a direct method. Comparing the membrane materials with different layers, the selectivity of the membrane is obviously improved along with the increase of the number of the cycles, the optimal value is obtained after 4 cycles, and the selectivity is reduced after 5 cycles.
Description
Technical Field
The invention belongs to the technical field of membrane materials and separation thereof, and particularly relates to a composite membrane material based on metal organic framework nanosheets and graphene oxide and application thereof in gas separation.
Background
The separation and purification process of the mixed materials is an important step in industrial production, consumes a large amount of energy and generates pollution along with the energy. The mixed gases generally have similar physical properties and molecular sizes, so the separation process has certain challenges. Compared with the traditional separation method, the membrane separation process has the advantages of energy conservation, high efficiency, easy operation, continuous work, small space and the like. Membrane materials are one of the cores of membrane separation processes, and ideally, separation membrane materials should have both high gas permeability and selectivity. Currently, the most studied membrane materials mainly include polymer membranes and inorganic membrane materials. Polymeric membranes have been widely used in the separation field because of their advantages such as ease of processing, low cost, etc. The pore size distribution of the polymeric membrane is not uniform and the plasticizing phenomenon is easy to occur, which affects the stability of the gas separation performance and cannot achieve high selectivity and permeability at the same time. The inorganic separation membrane is mainly a molecular sieve and a metal organic framework membrane material which are used for gas separation research, has uniform pore size distribution, can overcome the defects of a high molecular membrane, and simultaneously achieves high selectivity and permeability. Such inorganic microporous membrane materials are generally synthesized by hydrothermal or solvothermal synthesis, are not easy to process, and are high in cost. Researchers have prepared mixed matrix membranes by compounding high molecular and inorganic microporous materials as a solution in a short time.
In recent years, researchers have reduced the thickness of a film by preparing a film from two-dimensional materials (graphene oxide, molybdenum disulfide, molecular sieves, and metal organic framework nanosheets) to improve the performance of the film. There are still some problems with the composition of a single material, for example, a Graphene Oxide (GO) membrane permeates gas molecules by utilizing layer gaps and defects, so that selectivity is affected, and inorganic microporous material nanosheets with uniform pore channels are mainly prepared through an up-down peeling process, so that scale and yield are affected.
Disclosure of Invention
The invention aims to provide a composite membrane material based on metal organic framework nanosheets and graphene oxide, a preparation method and application thereof in gas separation. Firstly, preparing a metal oxide nanosheet at room temperature, paving the metal oxide nanosheet and graphene oxide dispersion liquid into a composite membrane material by a layer-by-layer method, wherein graphene oxide is used as a main body of the membrane, and the metal oxide nanosheet is doped in the graphene oxide. And reacting the obtained composite membrane material with an organic ligand to convert the composite membrane material into the graphene oxide composite membrane material doped with the metal organic framework nanosheets. By the strategy, while the ultrathin thickness is kept, the metal organic framework material with uniform pore channels is introduced into the membrane material, so that the separation selectivity is improved by 6 times compared with that of a pure graphene oxide membrane.
The metal-organic framework Material HKUST-1(Stephen S. -Y.Chui, Samuel M. -F.Lo, Jonathan P.H.Charant, A.Guy Orpen, Ian D.Williams, "A chemical functionalized Nanoporus Material [ Cu3(TMA)2(H2O)3]n", Science,1999,283,5405,1148-1150) is a propeller-type three-dimensional framework structure formed by metal copper ions and organic ligand trimesic acid (BTC), the size of a pore channel is 9 angstrom meters, each copper ion has a water molecule with weak coordination which can be removed to form unsaturated metal sites, and the membrane material has adsorption effect on carbon dioxide molecules, and improves the gas separation selectivity of the membrane material through selective adsorption.
The invention relates to a preparation method of a composite film material based on metal organic framework nanosheets and graphene oxide, which comprises the following steps:
(1) preparing graphene oxide solution
Mixing graphene oxide (analytically pure) and deionized water to prepare the graphene oxide with the concentration of 0.05-0.2 g.L-1The graphene oxide solution is ultrasonically dispersed uniformly, marked as solution A, and sealed and kept stand;
(2) preparing copper oxide nanosheet solution
Adding copper nitrate into deionized water to prepare the concentration1 to 3 mmol.L-1Copper nitrate solution of (1); adding ethanolamine into deionized water to prepare the mixture with the concentration of 1-2 mmol.L-1Ethanolamine solution of (a); mixing the two solutions in equal volume, reacting for 0.5-3 hours under closed magnetic stirring, and then standing for 20-30 hours in a closed manner at room temperature to obtain a copper oxide nanosheet solution, wherein the label is solution B;
(3) preparing ligand solution
Dissolving trimesic acid in a mixed solvent of ethanol and water to prepare a solution with the concentration of 0.5-2 mmol.L-1The trimesic acid solution of (a) is marked as solution C; wherein the volume ratio of ethanol to water is 1: 1, sealing and standing;
(4) method for preparing two-dimensional composite membrane by layer-by-layer method
Adding 5mL of solution A and solution B into a suction filtration device in sequence for suction filtration to complete 2-5 cycles; when the last circulation is completed and the film is completely drained, adding a layer of 1-10 mL solution A for capping, and completing primary film preparation after the film is completely drained; and then adding 10-50 mL of solution C into the suction filtration device, and converting the copper oxide nanosheet into HKUST-1, thereby obtaining the composite membrane material based on the metal organic framework nanosheet and the graphene oxide.
The composite membrane material of the invention can be widely used for mixed gas (H)2/CO2,CH4/CO2,N2/CO2) Especially for hydrogen and carbon dioxide.
The invention relates to relevant test conditions and methods:
scanning Electron Microscope (SEM) photograph: SEM used was a S4800 scanning electron microscope of Hitachi, Japan.
X-ray photoelectron diffraction (XRD) spectrum: the XRD test used was a LabX XRD-6000X-ray diffractometer from Shimadzu Shimazu, Japan. The Cu emission field was used, and the 2theta scan ranged from 4-40.
Atomic Force Microscope (AFM) photograph: MultiMode Scanning Probe Microscope.
Transmission Electron Microscope (TEM) photograph: JEM-2100 by JEOL, Japan Electron JEOL.
The gas separation test adopts a Wicke-Kallenbach Technique device (Angew. chem. int. Ed.2006,45, 7053-. The permeated gas was purged by a carrier gas into a gas chromatograph to examine various gas contents to determine the separation effect.
Gas Chromatography (GC) analysis: shimadzu GC 2014; column temperature: 50 ℃; a detector: TCD, wherein the volume ratio of the mixed gas is 1: 1 carbon dioxide and hydrogen.
Drawings
FIG. 1: XRD patterns of HKUST-1@ GO composite membranes in examples 1-4;
FIG. 2: front SEM photographs of the HKUST-1@ GO composite membranes of examples 1-4;
FIG. 3: SEM photographs of the cross sections of the HKUST-1@ GO composite membranes of examples 1-4;
comparing the simulated standard spectra in FIG. 1, the peak positions of the synthesized spectra were found to be consistent with the simulated standard spectra, indicating that the membrane materials prepared in examples 1-4 were doped with HKUST-1.
FIG. 2 is a front SEM photograph (right side view is an enlarged view of the left side view) of the HKUST-1@ GO composite membranes prepared in examples 1-4, a and b are 2 cycles, c and d are 3 cycles, e and f are 4 cycles, and g and h are 5 cycles. From the figure we can see that except for the defects found for HKUST-1@ GO-2 of the two cycles, the other cycles all resulted in a continuous flat membrane material.
FIG. 3 is a cross-sectional SEM photograph of the HKUST-1@ GO composite membranes prepared in examples 1-4. a is 2 cycles, b is 3 cycles, c is 4 cycles, and d is 5 cycles. The thickness of the membrane obtained from the figure is in the range of 100-300 nanometers, and the result shows that the ultra-thin membrane thickness is maintained while HKUST-1 with uniform pore channels is introduced.
Detailed Description
Example 1
(1) Preparing graphene oxide solution (solution A)
Purchase graphene oxide (analytically pure) product from pioneer nano corporation, and prepare 0.1 g.L from graphene oxide and deionized water-1The original graphene oxide concentration solution of (a). Will be preparedAnd placing the prepared graphene oxide raw solution in an ultrasonic disperser for ultrasonic dispersion, sealing and standing for later use.
(2) Preparing copper oxide nanosheet solution (solution B)
Accurately weighing copper nitrate in a beaker A by using an electronic balance, adding deionized water, stirring and accelerating dissolution to prepare 2mmol L-1(ii) a Preparing 1.6 mmol.L of beaker B with deionized water-1Ethanolamine solution, the solutions in beaker A and beaker B were mixed in equal volume. The cleaned and dried magneton is put into a mixed solution beaker along the wall of the beaker, and a layer of sealing film is covered to prevent the water from evaporating greatly. And placing the sealed mixed solution beaker on an electronic stirrer, stirring for 1 hour, and then placing the beaker in a vacuum drying oven at twenty-five ℃ for keeping the temperature for 24 hours. And sealing and standing for later use after the preparation of the copper oxide nanosheet solution is completed.
(3) Preparation of ligand solution (solution C)
Weighing BTC solid by an electronic balance to prepare 1 mmol.L-1The volume ratio of ethanol to water is 1: and 1, sealing and standing for later use.
(4) Method for preparing two-dimensional composite membrane by layer-by-layer method
The suction filtration device is cleaned and rinsed by deionized water, after drying, the suction filtration device is reasonably assembled, a nylon filter membrane (with the diameter of 47mm and the aperture of 200nm) is used as a substrate, after a clamp is ensured to be clamped, a water pump is opened, a large beaker is used for taking a proper amount of tap water and deionized water to respectively wash the tap water and the deionized water three times, a suction filtration head is taken down, water in a filter liquor bottle is poured out, and the suction filtration device is assembled again. After the preparation work is finished, a thin layer of deionized water is added on the sand core of the filter head, so that the nylon support layer can be placed stably without bubbles when being placed next step. Placing a nylon supporting layer, then placing a rubber gasket to prevent liquid leakage, assembling the rest parts, opening a water pump of a suction filtration device, pouring a proper amount of deionized water for leakage test, and reversely dismantling the device and smearing a little vacuum grease at the interface if water leakage occurs; if no water is leaked, the next step is continued.
5mL of solutions A and B were added to the suction filtration unit in sequence to complete 2 cycles. And when the last circulation is finished and the complete pumping is waited, continuously adding a layer of 5mL solution A for capping and waiting for complete pumping. And after the primary membrane preparation is finished, adding 25mL of solution C for conversion, and converting the copper oxide nanosheet into HKUST-1 to obtain the composite membrane HKUST-1@ GO-2.
(5) Characterization of the membranes
The powder X-ray diffraction pattern test, the scanning electron microscope, the transmission electron microscope and the atomic force microscope characterization and the mixed gas separation test are carried out on the powder X-ray diffraction pattern test, the scanning electron microscope and the transmission electron microscope, and the gas test results are shown in table 1.
Example 2
Steps (1) to (3) are the same as in example 1.
(4) Method for preparing two-dimensional composite membrane by layer-by-layer method
The suction filtration device installation and leak testing procedure was the same as in example 1. 5mL of solutions A and B were added to the suction filtration apparatus in sequence to complete 3 cycles. And when the last circulation is finished and the complete pumping is waited, continuously adding a layer of 5mL solution A for capping and waiting for complete pumping. After the primary membrane preparation is completed, 25mL of solution C needs to be added for conversion, and the copper oxide nanosheet in the doped reoxidized graphene is converted into HKUST-1, so that the composite membrane HKUST-1@ GO-3 is obtained.
(5) Characterization of the membranes
The powder X-ray diffraction pattern test, the scanning electron microscope, the transmission electron microscope and the atomic force microscope characterization and the mixed gas separation test are carried out on the powder X-ray diffraction pattern test, the scanning electron microscope and the transmission electron microscope, and the gas test results are shown in table 1.
Example 3
Steps (1) to (3) are the same as in example 1.
(4) Method for preparing two-dimensional composite membrane by layer-by-layer method
The suction filtration device installation and leak testing procedure was the same as in example 1. 5mL of solutions A and B were added to the suction filtration unit in sequence to complete 4 cycles. And when the last circulation is finished and the complete pumping is waited, continuously adding a layer of 5mL solution A for capping and waiting for complete pumping. After the primary membrane preparation is completed, 25mL of solution C needs to be added for conversion, and the copper oxide nanosheet in the doped reoxidized graphene is converted into HKUST-1, so that the composite membrane HKUST-1@ GO-4 is obtained.
(5) Characterization of the membranes
The powder X-ray diffraction pattern test, the scanning electron microscope, the transmission electron microscope and the atomic force microscope characterization and the mixed gas separation test are carried out on the powder X-ray diffraction pattern test, the scanning electron microscope and the transmission electron microscope, and the gas test results are shown in table 1.
Example 4
Steps (1) to (3) are the same as in example 1.
(4) Method for preparing two-dimensional composite membrane by layer-by-layer method
The suction filtration device installation and leak testing procedure was the same as in example 1. 5mL of solutions A and B were added to the suction filtration apparatus in sequence to complete 5 cycles. And when the last circulation is finished and the complete pumping is waited, continuously adding a layer of 5mL solution A for capping and waiting for complete pumping. After the primary membrane preparation is completed, 25mL of solution C needs to be added for conversion, and the copper oxide nanosheet in the doped reoxidized graphene is converted into HKUST-1, so that the composite membrane HKUST-1@ GO-5 is obtained.
(5) Characterization of the membranes
The powder X-ray diffraction pattern test, the scanning electron microscope, the transmission electron microscope and the atomic force microscope characterization and the mixed gas separation test are carried out on the powder X-ray diffraction pattern test, the scanning electron microscope and the transmission electron microscope, and the gas test results are shown in table 1.
Comparative example 1
Step (1) is the same as in example 1.
(2) Preparation of pure GO two-dimensional membranes
The suction filtration device installation and leak testing procedure was the same as in example 1. Add 25mL of solution a to the suction filtration device, wait for complete drainage to obtain pure GO membrane.
(3) Characterization of the membranes
The mixed gas separation test was performed, and the gas test results are shown in table 1.
Comparative example 2
Steps (1) to (3) are the same as in example 1.
(4) Direct mixing method for preparing two-dimensional composite membrane
The suction filtration device installation and leak testing procedure was the same as in example 1. After mixing the solutions A and B with equal volumes, 40mL of the mixed solution is added into a suction filtration device, and the solution is waited to be completely drained. After the primary membrane preparation is completed, 25mL of solution C needs to be added for conversion, and the copper oxide nanosheet in the doped reoxidized graphene is converted into HKUST-1, so that the composite membrane HKUST-1@ GO-m is obtained.
(5) Characterization of the membranes
The powder X-ray diffraction pattern test, the scanning electron microscope test and the mixed gas separation test were carried out on the powder X-ray diffraction pattern test, and the gas test results are shown in Table 1.
Table 1: gas separation performance data for membranes of examples 1-4 and comparative examples 1-2
Through comparison, the gas separation selectivity of the HKUST-1@ GO-4 membrane material is improved by about 6 times compared with that of a pure GO membrane, and the gas separation selectivity is also obviously improved compared with that of a membrane material obtained by a direct method. Comparing the membrane materials with different layers, the selectivity of the membrane is obviously improved along with the increase of the number of the cycles, the optimal value is obtained after 4 cycles, and the selectivity is reduced after 5 cycles.
Claims (4)
1. A preparation method of a composite film material based on metal organic framework nanosheets and graphene oxide comprises the following steps:
(1) preparing graphene oxide solution
Mixing graphene oxide and deionized water to prepare the graphene oxide with the concentration of 0.05-0.2 g.L-1The graphene oxide solution is ultrasonically dispersed uniformly, marked as solution A, and sealed and kept stand;
(2) preparing copper oxide nanosheet solution
Adding copper nitrate into deionized water to prepare the copper nitrate with the concentration of 1-3 mmol.L-1Copper nitrate solution of (1); adding ethanolamine into deionized water to prepare the mixture with the concentration of 1-2 mmol.L-1Ethanolamine solution of (a); mixing the two solutions in equal volume, reacting for 0.5-3 hours under closed magnetic stirring, and then standing for 20-30 hours in a closed manner at room temperature to obtain a copper oxide nanosheet solution, wherein the label is solution B;
(3) preparing ligand solution
Dissolving trimesic acid in a mixed solvent of ethanol and water to prepare a solution with the concentration of 0.5-2 mmol.L-1S-benzenediolAcid solution, labeled as solution C; wherein the volume ratio of ethanol to water is 1: 1, sealing and standing;
(4) method for preparing two-dimensional composite membrane by layer-by-layer method
Taking a nylon filter membrane as a substrate, sequentially adding 5mL of solution A and solution B into a suction filtration device for suction filtration, and completing 2-5 cycles; when the last circulation is completed and the film is completely drained, adding a layer of 1-10 mL solution A for capping, and completing primary film preparation after the film is completely drained; and then adding 10-50 mL of solution C into the suction filtration device, and converting the copper oxide nanosheet into HKUST-1, thereby obtaining the composite membrane material based on the metal organic framework nanosheet and the graphene oxide.
2. A composite film material based on metal organic framework nanosheets and graphene oxide is characterized in that: is prepared by the method of claim 1.
3. Use of a composite membrane material based on metal-organic framework nanosheets and graphene oxide according to claim 2 in gas separation.
4. The application of the composite membrane material based on the metal organic framework nano-sheets and the graphene oxide in gas separation, which is claimed in claim 3, is characterized in that: for separating hydrogen and carbon dioxide.
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| CN105688867A (en) * | 2016-03-10 | 2016-06-22 | 商丘师范学院 | Hexagonal prism type graphene-metal organic framework composite material as well as preparation method thereof |
| CN106256432A (en) * | 2016-08-03 | 2016-12-28 | 江苏大学 | A kind of water oxidation reaction catalyst based on metallic organic framework graphene oxide and preparation method thereof |
| CN106582317A (en) * | 2016-12-12 | 2017-04-26 | 北京工业大学 | Preparation method for metal organic framework modified graphene oxide lamellar structure composite membrane used for organic solvent nanofiltration |
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| RU2787343C1 (en) * | 2022-06-22 | 2023-01-09 | Иван Евгеньевич Горбань | Proton-exchange membrane based on organometallic framework structure hkust-1 |
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