CN117936866A - Metal organic framework/two-dimensional layered composite membrane as well as preparation method and application thereof - Google Patents
Metal organic framework/two-dimensional layered composite membrane as well as preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 119
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000012528 membrane Substances 0.000 title abstract description 20
- 238000004070 electrodeposition Methods 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000011065 in-situ storage Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000011888 foil Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 25
- 230000003204 osmotic effect Effects 0.000 claims description 23
- 238000010248 power generation Methods 0.000 claims description 23
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 20
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 17
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical group [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 17
- 238000000151 deposition Methods 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- -1 nitrogen heterocyclic compound Chemical class 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 238000005406 washing Methods 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004030 azacyclic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
- H01M8/227—Dialytic cells or batteries; Reverse electrodialysis cells or batteries
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
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- Composite Materials (AREA)
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Abstract
The invention discloses a metal organic framework/two-dimensional layered composite membrane, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Filtering the two-dimensional lamellar material dispersion liquid on a porous substrate to form a two-dimensional lamellar material@substrate film; (2) Attaching a two-dimensional layered material@substrate film to a metal foil electrode to serve as a working electrode of an anode electrodeposition system, taking a graphite electrode as a counter electrode, taking an organic ligand solution as electrodeposition liquid, performing electrochemical deposition reaction, growing a metal organic framework in situ between layers of the two-dimensional layered material, and forming a metal organic framework/two-dimensional layered composite film on a porous substrate; (3) And (3) cleaning and drying the product in the step (2), and carrying out on the porous substrate to obtain the flexible self-supporting metal-organic framework/two-dimensional layered composite film. The preparation method provided by the invention has the advantages of high efficiency, uniform composite dispersion of the prepared metal-organic framework/two-dimensional layered composite film and stable performance.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a metal-organic framework/two-dimensional layered composite film, and a preparation method and application thereof.
Background
In recent years, with the rapid development of nanotechnology and material science, two-dimensional materials have become a hot spot for research due to their unique physicochemical properties and wide application prospects. In particular, metal-organic frameworks are widely studied as a novel material having a high specific surface area, porosity and adjustable chemical properties for use in various fields of catalysis, gas storage, drug delivery, and the like.
However, it has been a challenge to effectively combine MOFs with two-dimensional materials to form a composite film that is stable and has excellent properties. In the prior art, the preparation method of the composite material of MOFs and two-dimensional materials comprises a self-assembly method, an in-situ growth method, a mechanical mixing method, a solvothermal/hydrothermal method, a layer-by-layer self-assembly method and the like. For example, chinese patent publication No. CN114649116a discloses a method for preparing an MXene/MOFs electrode material, wherein the method for preparing MXene/MOFs comprises: dropwise adding terephthalic acid solution into Ni (mixed solution of NO 3)2·6H2 O and MXene), mixing and stirring, adding triethylamine, stirring to obtain a precursor solution, heating the precursor solution, reacting for 8-12h, and treating after the reaction is finished to obtain an MXene/MOFs composite material, the Chinese patent document with publication No. CN116747718A discloses a preparation method of a two-dimensional bimetal MOF intercalated g-C 3N4 composite membrane, which comprises (1) preparing a bimetal layered MOF, mixing an aqueous solution of nickel acetate tetrahydrate and ferrous sulfate heptahydrate with an N, N-dimethylacetamide solution of terephthalic acid, performing hydrothermal reaction, cooling to room temperature, washing and drying to obtain a NiFe-MOF, (2) preparing the two-dimensional bimetal MOF intercalated g-C 3N4 composite membrane, dispersing NiFe-MOF and g-C 3N4 nano sheets into deionized water by ultrasonic, then vacuum filtering onto a microporous polyether sulfone membrane, and obtaining the two-dimensional bimetal intercalated g-C 3N4 composite membrane after heat setting.
Although the conventional methods such as self-assembly, in-situ growth, mechanical mixing, solvothermal/hydrothermal methods, and layer-by-layer self-assembly are widely used, they generally have problems of uneven material distribution, inaccurate structural control, low composite efficiency, and the like.
The application potential of MOFs and two-dimensional material composite materials in the fields of energy conversion and storage, especially in the technology of osmotic energy power generation, is not fully developed. Osmotic energy power generation is a technology for generating electric energy by utilizing osmotic pressure difference in solution, and has important significance for the sustainable energy field.
Disclosure of Invention
The invention provides a method for preparing a metal organic framework/two-dimensional layered composite film based on two-dimensional finite-field anodic electrodeposition, which has the advantages of high preparation efficiency, uniform composite dispersion of the prepared metal organic framework/two-dimensional layered composite film and stable performance.
The technical scheme of the invention is as follows:
A method for preparing a metal organic framework/two-dimensional layered composite film based on two-dimensional finite field anodic electrodeposition comprises the following steps:
(1) Filtering the two-dimensional lamellar material dispersion liquid on a porous substrate to form a two-dimensional lamellar material@substrate film;
(2) Attaching a two-dimensional layered material@substrate film to a metal foil electrode to serve as a working electrode of an anode electrodeposition system, taking a graphite electrode as a counter electrode, taking an organic ligand solution as electrodeposition liquid, performing electrochemical deposition reaction, growing Metal Organic Frameworks (MOFs) in situ between layers of the two-dimensional layered material, and forming a metal organic frameworks/two-dimensional layered composite film on a porous substrate;
(3) And (3) cleaning and drying the product in the step (2), and carrying out on the porous substrate to obtain the flexible self-supporting metal-organic framework/two-dimensional layered composite film.
According to the invention, through a unique anodic electrodeposition design, a metal ion source is provided by an anodic dissolution method after voltage is applied, and metal ions and organic ligands are mutually diffused at two sides of a two-dimensional layered material film, so that MOFs are formed in a two-dimensional layered structure, and a highly ordered and uniform metal-organic framework/two-dimensional layered composite film is generated.
Preferably, the two-dimensional layered material is at least one of graphene, molybdenum disulfide, two-dimensional carbide and nitride (MXene).
Preferably, the porous substrate is at least one of porous Anodic Aluminum Oxide (AAO), PVDF and PC porous film.
The MOF is selected based on its electrochemical properties and stability to accommodate the anodic electrodeposition process and subsequent application requirements. The choice of metal foil in the anodic electrodeposition system is based on the choice of MOF. The MOF is preferably a MOF that is structurally stable and easy to prepare.
Preferably, the organic ligand is at least one of an aromatic carboxylic acid and an azacyclic compound.
Preferably, the organic ligand is 2-methylimidazole and/or 2-amino terephthalic acid; the metal foil electrode is a Zn foil electrode and/or a Cu foil electrode.
Preferably, the metal organic framework is ZIF-8 and/or Cu-BDC-NH 2.
Preferably, in the electrodeposition process, the voltage is 0.1-3V, the deposition time is 0.1-24h, and the deposition temperature is 25-100 ℃.
The invention also provides the metal-organic framework/two-dimensional layered composite film prepared by the preparation method.
The metal-organic framework/two-dimensional layered composite film of the invention not only facilitates selective cation transport by forming a MOF layer with sub-nanoscale pores within a two-dimensional nanoconfinement space, but also significantly increases the charge density of the film by integration with the charge of the two-dimensional layered composite film surface. The combination of the structure and the charge characteristic ensures that the metal-organic framework/two-dimensional layered composite film keeps high ion selectivity in high-concentration solution, thereby effectively reducing the external resistance of the liquid storage and the internal resistance of the film and optimizing the osmotic energy power generation.
The invention also provides application of the metal-organic framework/two-dimensional layered composite film in osmotic energy power generation, and the metal-organic framework/two-dimensional layered composite film is used as an ion selective film material for osmotic energy power generation.
The osmotic energy power generation includes any form of generating electrical energy using osmotic pressure differences, particularly in the context of desalination of sea water, wastewater treatment, or other applications involving differences in solution concentrations.
According to the method, the MOFs and the deposition process of the two-dimensional materials (such as graphene and molybdenum disulfide) on the substrate are accurately controlled through an electrochemical means, so that more uniform material distribution and higher structural precision can be realized, and the in-situ growth of the highly ordered and uniform composite material is realized. In addition, the electrodeposition method has the characteristics of simple and convenient process, strong controllability and wide applicability, and provides a high-efficiency and reliable solution for preparing MOFs/two-dimensional material composite materials with excellent performances.
Compared with the prior art, the invention has the beneficial effects that:
(1) The stability and uniformity of the material are improved: through an accurately controlled electrodeposition diffusion process, the MOFs/two-dimensional material composite film with high uniformity and excellent stability can be manufactured, so that more reliable material selection is provided for practical application.
(2) Enhanced functionality and performance: the invention utilizes the two-dimensional finite field effect, not only increases the specific surface area of the composite material, but also improves the performance of the composite material in electrochemical application, in particular in the field of osmotic energy power generation.
(3) Extensive application potential: the method is not only limited to osmotic energy power generation, but also can be popularized to other fields, such as sensors, batteries, catalysts and the like, and has wide application prospects.
(4) Environmental friendly and cost effective: the method has advantages in environmental impact and cost effectiveness because the raw materials used by the method are easy to obtain, and the preparation process is simple and energy-saving.
In conclusion, the method not only improves the quality and performance of the material, but also opens up a new way for research and application of osmotic energy power generation and other related fields, and has important technical and economic values.
Drawings
FIG. 1 is a schematic diagram of an anodic electrodeposition apparatus based on a two-dimensional confinement;
FIG. 2 is a schematic illustration of a diffusion mechanism of in-situ growth of two-dimensional layered materials based on two-dimensional confinement of anodic electrodeposition MOFs;
FIG. 3 is a SEM photograph of a cross section of a ZIF-8@GO composite film grown in situ by two-dimensional domain-based anodic electrodeposition of example 1;
FIG. 4 is a TEM photograph of a cross section of a ZIF-8@GO composite film grown in situ by two-dimensional domain-based anodic electrodeposition of example 1;
FIG. 5 is a schematic diagram of an apparatus for osmotic energy power generation of a two-dimensional confinement-based anodic electrodeposition in-situ grown ZIF-8@GO composite membrane;
FIG. 6 is a graph of power generation performance data for two-dimensional-confinement-based anodic electrodeposition in-situ grown ZIF-8@GO composite films of example 7 for osmotic power generation.
Detailed Description
The following examples were electrodeposited using an electrodeposition apparatus as shown in fig. 1, with a graphite electrode on the left as the cathode, a two-dimensional layered material on the right as the anode, and Pt sheets drawn through Pt wires.
Ion diffusion during electrodeposition is shown in fig. 2. Wherein the ligand diffuses into the two-dimensional layered material from the direction of the electrodeposition liquid, and the metal ions oxidized from the metal foil diffuse into the two-dimensional layered material from the opposite direction, thereby realizing the in-situ nucleation growth of MOF crystal grains in the two-dimensional layered material.
Example 1
An anodic electrodeposition preparation method of a metal organic framework/two-dimensional layered composite membrane for osmotic energy power generation comprises the following steps:
(1) Preparing a dispersion liquid from a two-dimensional graphene oxide material at a concentration of 0.01mg/ml, and fully and uniformly mixing the dispersion liquid through ultrasonic treatment. And then, carrying out suction filtration on the dispersion liquid to a porous PVDF substrate by utilizing a vacuum suction filtration technology, so as to prepare the GO@PVDF substrate film.
(2) Taking a pretreated GO@PVDF substrate film; then, the composite film is used in a double-electrode deposition system and is tightly attached to a metal Zn foil electrode to serve as a working electrode of an anode electrodeposition system, and meanwhile, a graphite electrode is used as a counter electrode and a 2-methylimidazole solution is used as an electrodeposition liquid.
(3) An electrodeposition bath was configured with the following parameters:
2-methylimidazole was dissolved in a mixed solvent of deionized water and N, N-dimethylformamide (volume ratio: 1:1) at a concentration of 0.3mol/L.
(4) Applying a voltage of 1V to the system with the aid of an electrochemical workstation to initiate an electrochemical deposition reaction; finally, after electrochemical treatment at the preset temperature of 60 ℃ for 12 hours, the Metal Organic Frameworks (MOFs) are grown in situ between two-dimensional material layers, and the ZIF-8@GO composite film is formed.
(5) After the preparation of MOFs/two-dimensional layered composite film by electrochemical deposition, methanol is used for repeatedly washing the composite film until no obvious MOFs large particles remain on the surface of the composite film. After the above-mentioned washing treatment, the composite film is subjected to drying treatment. And (3) gently tearing the dried ZIF-8@GO composite film from the substrate to obtain the flexible self-supporting composite film.
The scanning electron microscope and the transmission electron microscope pictures of the cross section of the prepared ZIF-8@GO composite film are respectively shown in fig. 3 and fig. 4. As can be seen from fig. 3 and fig. 4, the MOF layer with sub-nano pores is formed in the two-dimensional nano confinement space in the ZIF-8@go composite film, and the material is uniformly dispersed and has a highly ordered structure.
Example 2
An anodic electrodeposition preparation method of a metal organic framework/two-dimensional layered composite membrane for osmotic energy power generation comprises the following steps:
(1) The two-dimensional MXene material is prepared into dispersion liquid at the concentration of 0.01mg/ml, and the dispersion liquid is fully and uniformly mixed by ultrasonic treatment. Then, the dispersion is filtered onto a porous PVDF substrate by vacuum filtration technology, thereby preparing the MXene@PVDF substrate film.
(2) Taking a pretreated MXene@PVDF substrate film; then, the composite film is used in a double-electrode deposition system and is tightly attached to a metal Zn foil electrode to serve as a working electrode of an anode electrodeposition system, and meanwhile, a graphite electrode is used as a counter electrode and a 2-methylimidazole solution is used as an electrodeposition liquid.
(3) An electrodeposition bath was configured with the following parameters:
2-methylimidazole was dissolved in a mixed solvent of deionized water and N, N-dimethylformamide (volume ratio: 1:1) at a concentration of 0.3mol/L.
(4) Applying a voltage of 1V to the system with the aid of an electrochemical workstation to initiate an electrochemical deposition reaction; finally, after electrochemical treatment at the preset temperature of 60 ℃ for 12 hours, the Metal Organic Frameworks (MOFs) are grown in situ between two-dimensional material layers, and the ZIF-8@MXene composite film is formed.
(5) After the preparation of MOFs/two-dimensional layered composite film by electrochemical deposition, methanol is used for repeatedly washing the composite film until no obvious MOFs large particles remain on the surface of the composite film. After the above-mentioned washing treatment, the composite film is subjected to drying treatment. The dried ZIF-8@MXene composite film was gently removed from the substrate to obtain a flexible self-supporting composite film.
Example 3
An anodic electrodeposition preparation method of a metal organic framework/two-dimensional layered composite membrane for osmotic energy power generation comprises the following steps:
(1) Preparing a dispersion liquid from a two-dimensional graphene oxide material at a concentration of 0.01mg/ml, and fully and uniformly mixing the dispersion liquid through ultrasonic treatment. And then, carrying out suction filtration on the dispersion liquid to a porous PVDF substrate by utilizing a vacuum suction filtration technology, so as to prepare the GO@PVDF substrate film.
(2) Taking a pretreated GO@PVDF substrate film; then, the composite film is used in a double-electrode deposition system and is tightly attached to a metal Cu foil electrode to serve as a working electrode of an anode electrodeposition system, meanwhile, a graphite electrode is used as a counter electrode, and a 2-amino terephthalic acid (H 2BDC-NH2) solution is used as an electrodeposition liquid.
(3) An electrodeposition bath was configured with the following parameters:
h 2BDC-NH2 was dissolved in N, N-dimethylformamide solvent at a concentration of 0.1mol/L.
(4) Applying a voltage of 2V to the system with the aid of an electrochemical workstation to initiate an electrochemical deposition reaction; finally, after electrochemical treatment at the preset temperature of 110 ℃ for 12 hours, the in-situ growth of Metal Organic Frameworks (MOFs) between two-dimensional material layers is realized, and the Cu-BDC-NH 2 @GO composite film is formed.
(5) After the preparation of MOFs/two-dimensional layered composite film by electrochemical deposition, methanol is used for repeatedly washing the composite film until no obvious MOFs large particles remain on the surface of the composite film. After the above-mentioned washing treatment, the composite film is subjected to drying treatment. And (3) gently tearing the dried Cu-BDC-NH 2 @GO composite film from the substrate to obtain the flexible self-supporting composite film.
Example 4
An anodic electrodeposition preparation method of a metal organic framework/two-dimensional layered composite membrane for osmotic energy power generation comprises the following steps:
(1) The two-dimensional MXene material is prepared into dispersion liquid at the concentration of 0.01mg/ml, and the dispersion liquid is fully and uniformly mixed by ultrasonic treatment. Then, the dispersion is filtered onto a porous PVDF substrate by vacuum filtration technology, thereby preparing the MXene@PVDF substrate film.
(2) Taking a pretreated MXene@PVDF substrate film; then, the composite film is used in a double-electrode deposition system and is tightly attached to a metal Cu foil electrode to serve as a working electrode of an anode electrodeposition system, meanwhile, a graphite electrode is used as a counter electrode, and a 2-amino terephthalic acid (H 2BDC-NH2) solution is used as an electrodeposition liquid.
(3) An electrodeposition bath was configured with the following parameters:
h 2BDC-NH2 was dissolved in N, N-dimethylformamide solvent at a concentration of 0.1mol/L.
(4) Applying a voltage of 2V to the system with the aid of an electrochemical workstation to initiate an electrochemical deposition reaction; finally, after electrochemical treatment at the preset temperature of 110 ℃ for 12 hours, the in-situ growth of Metal Organic Frameworks (MOFs) between two-dimensional material layers is realized, and the Cu-BDC-NH 2 @MXene composite film is formed.
(5) After the preparation of MOFs/two-dimensional layered composite film by electrochemical deposition, methanol is used for repeatedly washing the composite film until no obvious MOFs large particles remain on the surface of the composite film. After the above-mentioned washing treatment, the composite film is subjected to drying treatment. The dried Cu-BDC-NH 2 @ MXene composite film was gently removed from the substrate to obtain a flexible self-supporting composite film.
Example 5
An anodic electrodeposition preparation method of a metal organic framework/two-dimensional layered composite membrane for osmotic energy power generation comprises the following steps:
(1) Preparing a dispersion liquid from a two-dimensional graphene oxide material at a concentration of 0.01mg/ml, and fully and uniformly mixing the dispersion liquid through ultrasonic treatment. And then, carrying out suction filtration on the dispersion liquid to a porous AAO substrate by utilizing a vacuum suction filtration technology, so as to prepare the GO@AAO substrate film.
(2) Taking a pretreated GO@AAO substrate film; then, the composite film is used in a double-electrode deposition system and is tightly attached to a metal Cu foil electrode to serve as a working electrode of an anode electrodeposition system, meanwhile, a graphite electrode is used as a counter electrode, and a 2-amino terephthalic acid (H 2BDC-NH2) solution is used as an electrodeposition liquid.
(3) An electrodeposition bath was configured with the following parameters:
h 2BDC-NH2 was dissolved in N, N-dimethylformamide solvent at a concentration of 0.1mol/L.
(4) Applying a voltage of 2V to the system with the aid of an electrochemical workstation to initiate an electrochemical deposition reaction; finally, after electrochemical treatment at the preset temperature of 110 ℃ for 12 hours, the in-situ growth of Metal Organic Frameworks (MOFs) between two-dimensional material layers is realized, and the Cu-BDC-NH 2 @GO composite film is formed.
(5) After the preparation of MOFs/two-dimensional layered composite film by electrochemical deposition, methanol is used for repeatedly washing the composite film until no obvious MOFs large particles remain on the surface of the composite film. After the above-mentioned washing treatment, the composite film is subjected to drying treatment. And (3) gently tearing the dried Cu-BDC-NH 2 @GO composite film from the substrate to obtain the flexible self-supporting composite film.
Example 6
An anodic electrodeposition preparation method of a metal organic framework/two-dimensional layered composite membrane for osmotic energy power generation comprises the following steps:
(1) Preparing a dispersion liquid from a two-dimensional graphene oxide material at a concentration of 0.01mg/ml, and fully and uniformly mixing the dispersion liquid through ultrasonic treatment. And then, carrying out suction filtration on the dispersion liquid to a porous PVDF substrate by utilizing a vacuum suction filtration technology, so as to prepare the GO@PVDF substrate film.
(2) Taking a pretreated GO@PVDF substrate film; then, the composite film is used in a double-electrode deposition system and is tightly attached to a metal Zn foil electrode to serve as a working electrode of an anode electrodeposition system, and meanwhile, a graphite electrode is used as a counter electrode and a 2-methylimidazole solution is used as an electrodeposition liquid.
(3) An electrodeposition bath was configured with the following parameters:
2-methylimidazole was dissolved in a mixed solvent of deionized water and N, N-dimethylformamide (volume ratio: 1:1) at a concentration of 0.3mol/L.
(4) Applying a voltage of 1V to the system with the aid of an electrochemical workstation to initiate an electrochemical deposition reaction; finally, after electrochemical treatment at the preset temperature of 60 ℃ for 6 hours, the Metal Organic Frameworks (MOFs) are grown in situ between two-dimensional material layers, and the ZIF-8@GO composite film is formed.
(5) After the preparation of MOFs/two-dimensional layered composite film by electrochemical deposition, methanol is used for repeatedly washing the composite film until no obvious MOFs large particles remain on the surface of the composite film. After the above-mentioned washing treatment, the composite film is subjected to drying treatment. And (3) gently tearing the dried ZIF-8@GO composite film from the substrate to obtain the flexible self-supporting composite film.
Example 7
An anodic electrodeposition preparation method of a metal organic framework/two-dimensional layered composite membrane for osmotic energy power generation comprises the following steps:
(1) Preparing a dispersion liquid from a two-dimensional graphene oxide material at a concentration of 0.01mg/ml, and fully and uniformly mixing the dispersion liquid through ultrasonic treatment. And then, carrying out suction filtration on the dispersion liquid to a porous PVDF substrate by utilizing a vacuum suction filtration technology, so as to prepare the GO@PVDF substrate film.
(2) Taking a pretreated GO@PVDF substrate film; then, the composite film is used in a double-electrode deposition system and is tightly attached to a metal Zn foil electrode to serve as a working electrode of an anode electrodeposition system, and meanwhile, a graphite electrode is used as a counter electrode and a 2-methylimidazole solution is used as an electrodeposition liquid.
(3) An electrodeposition bath was configured with the following parameters:
2-methylimidazole was dissolved in a mixed solvent of deionized water and N, N-dimethylformamide (volume ratio: 1:1) at a concentration of 0.3mol/L.
(4) Applying a voltage of 1V to the system with the aid of an electrochemical workstation to initiate an electrochemical deposition reaction; finally, after electrochemical treatment at the preset temperature of 60 ℃ for 6 hours, the Metal Organic Frameworks (MOFs) are grown in situ between two-dimensional material layers, and the ZIF-8@GO composite film is formed.
(5) After the preparation of MOFs/two-dimensional layered composite film by electrochemical deposition, methanol is used for repeatedly washing the composite film until no obvious MOFs large particles remain on the surface of the composite film. After the above-mentioned washing treatment, the composite film is subjected to drying treatment. And (3) gently tearing the dried ZIF-8@GO composite film from the substrate to obtain the flexible self-supporting composite film.
The ZIF-8@GO composite film prepared in the embodiment 7 is assembled into the osmotic energy power generation device shown in fig. 5, the high-concentration KCl solution is arranged on the left side, the low-concentration KCl solution is arranged on the right side, the composite film plays a role in selective ion transmission in the middle, and generated electric energy is led out through an electrode and stored.
In osmotic power generation devices, the composite membrane is used as the core ion-selective channel to generate electrical energy using a concentration gradient between fresh water and brine. When fresh water is mixed with brine on both sides of the membrane, the sub-nano-pores promote selective transport of cations, while the high charge density of GO enhances ion selectivity.
As shown in fig. 6, by changing the magnitude of the external load resistor and the concentration difference of the solution on both sides of the membrane,
And performing a penetration energy power generation test. The different lines in the graph represent the output power data as a function of load resistance for different solution concentration differences. In the test, the composite membrane exhibited excellent performance at a 10-fold concentration gradient (simulating the concentration difference between river water and sea water).
As can be seen from fig. 6, the device achieves a maximum output power of 6.82 microwatts at a load resistance of 5000 ohms, and more importantly, its effective test area is 12.56mm 2, which is much higher than the test area in the current literature (0.03 mm 2). In large area applications, the composite films exhibit excellent performance and stability, enabling power to be supplied to a wide variety of electronic devices, ranging from LEDs to digital clocks and portable gaming devices. These findings highlight the potential of biomimetic ion channel membranes in sustainable energy applications and in a wider energy harvesting technology field.
The foregoing embodiments have described the technical solutions and advantages of the present invention in detail, and it should be understood that the foregoing embodiments are merely illustrative of the present invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like that fall within the principles of the present invention should be included in the scope of the invention.
Claims (9)
1. The method for preparing the metal organic framework/two-dimensional layered composite film based on the two-dimensional finite field anodic electrodeposition is characterized by comprising the following steps of:
(1) Filtering the two-dimensional lamellar material dispersion liquid on a porous substrate to form a two-dimensional lamellar material@substrate film;
(2) Attaching a two-dimensional layered material@substrate film to a metal foil electrode to serve as a working electrode of an anode electrodeposition system, taking a graphite electrode as a counter electrode, taking an organic ligand solution as electrodeposition liquid, performing electrochemical deposition reaction, growing a metal organic framework in situ between layers of the two-dimensional layered material, and forming a metal organic framework/two-dimensional layered composite film on a porous substrate;
(3) And (3) cleaning and drying the product in the step (2), and carrying out on the porous substrate to obtain the flexible self-supporting metal-organic framework/two-dimensional layered composite film.
2. The method for preparing the metal-organic framework/two-dimensional layered composite film by two-dimensional domain-based anodic electrodeposition according to claim 1, wherein the two-dimensional layered material is at least one of graphene, molybdenum disulfide, two-dimensional carbide and nitride.
3. The method for preparing the metal-organic framework/two-dimensional layered composite film by two-dimensional domain-based anodic electrodeposition according to claim 1, wherein the porous substrate is at least one of porous anodic aluminum oxide, PVDF and PC porous films.
4. The method for preparing a metal-organic framework/two-dimensional layered composite film by two-dimensional domain-based anodic electrodeposition according to claim 1, wherein the organic ligand is at least one of aromatic carboxylic acid and nitrogen heterocyclic compound.
5. The method for preparing a metal-organic framework/two-dimensional layered composite film based on two-dimensional domain-based anodic electrodeposition according to claim 4, wherein the organic ligand is 2-methylimidazole and/or 2-amino terephthalic acid; the metal foil electrode is a Zn foil electrode and/or a Cu foil electrode.
6. The method for preparing the metal-organic framework/two-dimensional layered composite film by two-dimensional domain-based anodic electrodeposition according to claim 5, wherein the metal-organic framework is ZIF-8 and/or Cu-BDC-NH 2.
7. The method for preparing the metal-organic framework/two-dimensional layered composite film by two-dimensional domain-based anodic electrodeposition according to claim 1, wherein the voltage is 0.1-3V, the deposition time is 0.1-24h, and the deposition temperature is 25-100 ℃.
8. A metal organic framework/two-dimensional layered composite film prepared by the method of any one of claims 1-7.
9. Use of the metal-organic framework/two-dimensional layered composite film according to claim 8 as an ion-selective film material for osmotic power generation.
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