CN116478502A - Two-dimensional single-layer ionic COF and application thereof in osmotic energy conversion - Google Patents
Two-dimensional single-layer ionic COF and application thereof in osmotic energy conversion Download PDFInfo
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- 239000002356 single layer Substances 0.000 title claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 36
- 230000003204 osmotic effect Effects 0.000 title claims abstract description 30
- 150000002500 ions Chemical class 0.000 claims abstract description 49
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 45
- ZMMJGEGLRURXTF-UHFFFAOYSA-N ethidium bromide Chemical compound [Br-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 ZMMJGEGLRURXTF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960005542 ethidium bromide Drugs 0.000 claims abstract description 17
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002262 Schiff base Substances 0.000 claims abstract description 8
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 8
- 150000002466 imines Chemical class 0.000 claims abstract description 3
- 230000004888 barrier function Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical group OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 238000010248 power generation Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000935 solvent evaporation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 239000011148 porous material Substances 0.000 abstract description 10
- 230000004907 flux Effects 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 239000013310 covalent-organic framework Substances 0.000 description 58
- 239000000243 solution Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- AOBBDXYJJKBZJY-UHFFFAOYSA-N 2,2,3,3-tetrafluorobutane-1,4-diamine Chemical compound NCC(F)(F)C(F)(F)CN AOBBDXYJJKBZJY-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002211 ultraviolet spectrum Methods 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000010884 ion-beam technique Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 nitrogen cations Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QCWPXJXDPFRUGF-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 QCWPXJXDPFRUGF-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005139 ultra-violet Raman spectroscopy Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/30—Energy from the sea, e.g. using wave energy or salinity gradient
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Abstract
The invention discloses a two-dimensional single-layer ionic COF and application thereof in osmotic energy conversion. The two-dimensional single-layer ionic COF film is polymerized by forming imine covalent bonds through Schiff base reaction of 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin and ethidium bromide; the thickness is 0.9-1.1 nm, and the aperture is 1.6-1.8 nm. The two-dimensional s-iCOF material is formed by covalently connecting 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin and ethidium bromide, and has larger porosity, good integrity, regular pore canal arrangement and electropositivity. In osmotic energy conversion, the larger porosity and regular pore arrangement ensures a considerable ion flux, good integrity and monolayer properties ensure high energy conversion, while positively charged surfaces indicate that ions can be selectively transported for larger output potentials. In summary, the analysis results show that extremely excellent output power can be obtained by osmotic energy conversion from two-dimensional s-iCOF.
Description
Technical Field
The invention relates to a two-dimensional single-layer ionic COF and application thereof in osmotic energy conversion, belonging to the technical field of osmotic energy conversion.
Background
The osmotic energy between solutions of different salt concentrations is considered to be a renewable clean energy source. By utilizing the reverse electrodialysis technology, the osmotic energy is converted into electric energy, and the dependence of people on non-renewable energy sources is greatly relieved. In recent years, a selectively permeable membrane based on graphene oxide, molybdenum disulfide, a metal organic frame, or the like is widely used in the field of osmotic energy conversion because of being capable of selectively transporting ions, but still faces the problem that it cannot have both high permeability and high ion selectivity, and thus the improvement of osmotic energy conversion efficiency thereof is limited. Thus, developing new porous membranes to achieve the trade-off of ion selectivity and permeability remains one of the great challenges in the field of osmotic energy conversion.
Disclosure of Invention
The invention aims to provide a two-dimensional single-layer ionic covalent organic framework (single-layer ionic covalent-organic framework, s-iCOF) and application thereof in osmotic energy conversion, and the s-iCOF is used as an energy conversion film, so that the output power of osmotic energy conversion can be obviously improved, and the technical problem in the osmotic energy conversion field can be solved to a certain extent.
The two-dimensional single-layer ionic COF film is obtained by polymerizing 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin (TFPP) and Ethidium Bromide (EB) through Schiff base reaction to form imine covalent bonds.
The thickness of the two-dimensional single-layer ion type COF film is 0.9-1.1 nm, preferably 1nm, and the pore diameter is 1.6-1.8 nm, preferably 1.7nm.
The two-dimensional single-layer ionic COF film has continuous and orderly arranged nano channels, high surface charge density and extremely low thickness, and the excellent properties further improve the selectivity and permeability of anions and cations. The positive charges exposed on the surface of the two-dimensional single-layer ion type COF film can be utilized to better have selectivity on anions, the single-layer thickness and the high porosity can enable the ions to have the lowest internal resistance and high ion flux during ion transmission, and the reliability of the single-layer film is also measured on the surface of the two-dimensional Young modulus. Therefore, the two-dimensional single-layer ion type COF film is used as a permeation energy conversion film, and the permeation energy output power can be greatly improved.
In a preferred embodiment, the two-dimensional single-layer ionic COF film has positive charges and a charge density of 4.4mC/m 2 The two-dimensional single-layer ion type COF membrane can be used as a permeable power generation diaphragm by matching with extremely low thickness and aperture, so that the output power can be effectively improved to kilowatt level.
In a preferred embodiment, the two-dimensional single-layer ion type COF film of the present invention can output 1062 W.m at sodium chloride concentrations of 0.5M and 0.01M, respectively, attached to a silicon nitride perforated substrate having a diameter of 1. Mu.m -2 。
The invention also provides a preparation method of the two-dimensional single-layer ionic COF film, which comprises the following steps:
dripping ethidium bromide and a catalyst into the uniformly spread 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin monolayer, and obtaining the two-dimensional single-layer ionic COF film through Schiff base reaction.
Wherein the molar ratio of the 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin to the ethidium bromide is 1: 100-1: 200, preferably 1:200, increasing the quantity of EB is beneficial to the formation of a large-area single-layer ion COF film;
the catalyst is trifluoroacetic acid or glacial acetic acid, and can catalyze dehydration condensation of aldehyde groups and amino groups to form imine bonds;
the Schiff base reaction time is 24 hours.
Preferably, the 5,10,15, 20-tetrakis (4-aldehydephenyl) -21h,23 h-porphyrin monolayer is prepared according to the following steps:
dropwise adding the solution of the 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin into a drawing instrument through a microsyringe, and sequentially performing solvent evaporation and sliding barrier compression to obtain the 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin monolayer;
the solvent is evaporated for 20-40 min, preferably 30min;
the surface tension of the 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin monomolecular layer is 9-11 mN/m, preferably 10mN/m through the sliding barrier compression, under the condition, TFPP molecules can be uniformly and flatly paved on the water surface in a single molecule form, and the occurrence of the next polymerization reaction is facilitated.
The invention utilizes the uniformly distributed aldehyde groups of TFPP and the symmetrically distributed amino groups of EB, so that the two can form a large-area reticular structure through imine bonds; in addition, EB molecules carry nitrogen cations and can selectively transport anions.
The two-dimensional s-iCOF material is formed by covalently connecting 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin and ethidium bromide, and has larger porosity, good integrity, regular pore canal arrangement and electropositivity. In osmotic energy conversion, the larger porosity and regular pore arrangement ensures a considerable ion flux, good integrity and monolayer properties ensure high energy conversion, while positively charged surfaces indicate that ions can be selectively transported for larger output potentials. In summary, the analysis results show that extremely excellent output power can be obtained by osmotic energy conversion from two-dimensional s-iCOF.
Drawings
FIG. 1 is a graph showing the surface tension of the s-iCOF synthesized in example 1 of the present invention;
FIG. 2 is a Zeta potential diagram of the s-iCOF and s-COF synthesized in example 1 of the present invention;
FIG. 3 is a graph showing the experimental contact angle of the s-iCOF synthesized in example 1 of the present invention;
FIG. 4 is a photomicrograph of the s-iCOF synthesized in example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of the s-iCOF synthesized in example 1 of the present invention;
FIG. 6 is a transmission electron microscope topography of the s-iCOF synthesized in example 1 of the present invention;
FIG. 7 is a high resolution frozen transmission electron microscope image of the s-iCOF synthesized in example 1 of the present invention;
FIG. 8 is an atomic force microscope image of an s-iCOF synthesized in example 1 of the present invention;
FIG. 9 is an imaging of the elemental composition of the synthetic s-iCOF of example 1 of the present invention;
FIG. 10 is an X-ray photoelectron spectrum of an s-iCOF synthesized in example 1 of the present invention;
FIG. 11 is a Raman spectrum of s-iCOF synthesized in example 1 of the present invention;
FIG. 12 is an ultraviolet spectrum of the s-iCOF synthesized in example 1 of the present invention;
FIG. 13 is an ion selectivity test for the synthetic s-iCOF of example 1 of the present invention;
FIG. 14 is a graph showing the osmotic energy power density test of the synthetic s-iCOF of example 1 of the present invention;
FIG. 15 shows the concentration difference I-V test of the nonionic two-dimensional single-layer COF film synthesized in comparative example 1 of the present invention.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
According to the invention, the ionic COF can be effectively synthesized by Schiff base reaction by taking TFPP and EB as monomers of a COF framework. The film material can distort the conformation due to the existence of surface charge to generate aperture of 1.7nm, which is more favorable for overlapping of double electric layers and has potential to be used as an osmotic energy conversion film to further improve the power generation. In addition, as the film has monoatomic layer level thickness, the selectivity and permeability of positive and negative ions in salt solution can be greatly improved, so that the output power is further improved.
The invention provides a preparation method of a two-dimensional single-layer ion COF, which comprises the following steps:
firstly, a chloroform solution of TFPP is sucked by a microsyringe and slowly dropped on a plane of a Langmuir-Blodgett drawing instrument filled with secondary water in a symmetrical W mode, and the solvent is evaporated. After the solvent evaporates and after the surface tension indication is stable, the sliding barrier compression molecular layer slowly moves to finally lead the surface tension to reach 10mN/m. And (3) slowly dripping 2mL of 4.1mmol/L EB solution to the two sides of the reaction tank when the sliding barrier stops. And standing for 24 hours to obtain a two-dimensional s-iCOF film, transferring the COF layer onto a silicon nitride window substrate by using a dipping method, and soaking with chloroform and secondary water. After the water is evaporated, the substrate is clamped by the clamping groove and is packaged by ultraviolet curing glue to avoid liquid leakage. By placing the silicon nitride substrate between the two tanks, respectively injecting 0.5M and 0.01M NaCl solution therein, and placing the Ag/AgCl salt bridge electrode therein, the corresponding I-V curve can be obtained.
Comparative example 1,
The Langmuir-Blodgett drawing instrument was rinsed with ethanol and secondary water and the tank was filled with secondary water to a level 1-2 mm above the tank surface. The platinum sheet is washed by ethanol, and then is placed on an alcohol lamp to burn and remove organic residues, and then is placed on a hook to enable the platinum sheet to be semi-immersed in the water surface. Then 30. Mu.L of TFPP in chloroform solution was pipetted by a microsyringe and slowly dropped in a "W" to the water surface to spread the molecules as much as possible and left for 30min to evaporate the solvent. After the surface tension is stable, the sliding barrier is slowly moved at a speed of 1mm/min to continuously compress so that TFPP molecules are closely arranged on the water surface until the surface tension reaches 10mN/m. And finally, 1mL of 4.1mM p-phenylenediamine solution is respectively dripped on two sides of the sliding barrier, and the two-dimensional single-layer COF film is obtained after 24 hours of reaction.
Example 1,
The Langmuir-Blodgett drawing instrument was rinsed with ethanol and secondary water and the tank was filled with secondary water to a level 1-2 mm above the tank surface. The platinum sheet is washed by ethanol, and then is placed on an alcohol lamp to burn and remove organic residues, and then is placed on a hook to enable the platinum sheet to be semi-immersed in the water surface. Then 30. Mu.L of TFPP in chloroform solution was pipetted by a microsyringe and slowly dropped in a "W" to the water surface to spread the molecules as much as possible and left for 30min to evaporate the solvent. After the surface tension is stable, the sliding barrier is slowly moved at a speed of 1mm/min to continuously compress so that TFPP molecules are closely arranged on the water surface until the surface tension reaches 10mN/m. And finally, 1mL of 4.1mM ethidium bromide solution is respectively dripped on two sides of the sliding barrier, and the two-dimensional single-layer COF film is obtained after 24 hours of reaction.
The properties of the two-dimensional single-layer ion COF prepared in example 1 and comparative example 1 were measured as follows:
frozen high resolution transmission electron microscopy assay: and placing the two-dimensional single-layer ion COF on a copper mesh, and measuring the lattice fringes, the pore size and the corresponding diffraction points of the two-dimensional single-layer ion COF.
Atomic force microscopy measurements: and placing the two-dimensional single-layer ion COF on a silicon wafer, and naturally drying the silicon wafer. The material thickness was measured where the material edge was found under the mirror.
Two-dimensional young's modulus measurement: the two-dimensional single-layer ion COF was placed on a silicon window having a diameter of 1.8 μm and allowed to dry naturally. The two-dimensional Young's modulus was measured by finding the corresponding Kong Daochu under a mirror.
Surface potential measurement: the two-dimensional single-layer ion COF was placed on a silicon wafer, immersed in a 0.01M KCl solution, and its surface potential was measured.
Contact angle measurement: the two-dimensional single-layer ion COF is placed on a silicon wafer, the whole body is placed on an instrument platform, water drops are slowly dripped into the single-layer ion COF, and the corresponding contact angle of the single-layer ion COF is measured.
Ultraviolet spectrum measurement: the two-dimensional single-layer ion COF was placed on a quartz substrate, placed in a groove, and its ultraviolet spectrum was measured.
Raman spectrometry: the two-dimensional single-layer ion COF is placed on a gold-plated silicon wafer, and a 532nm wavelength light source is adopted to measure the Raman spectrum.
Determination of X-ray photoelectron Spectrometry: the two-dimensional single-layer ion COF was placed on a silicon wafer, and the X-ray photoelectron spectrum of the two-dimensional single-layer ion COF was measured.
Determination of ion selectivity: a focused ion beam system was used to etch a hole of 100nm diameter in the silicon nitride window and place a two-dimensional monolayer of ion COF thereon. After the material is naturally dried, the material is placed between potassium chloride solutions with different concentrations, and an Ag/AgCl salt bridge electrode is adopted to measure the osmotic voltage and the osmotic current through scanning an I-V curve.
And (3) measuring osmotic power generation: a focused ion beam system was used to etch a hole of 1 μm diameter in the silicon nitride window and place a two-dimensional monolayer of ion COF thereon. After the material has dried naturally, it is placed between 0.5M and 0.01M sodium chloride solution and connected to the resistor inside and outside the loop. And measuring the penetration voltage and the penetration current by adopting an Ag/AgCl salt bridge electrode through scanning an I-V curve by changing the resistance value, and calculating corresponding output power and maximum power.
For this system, the following formula p=i is used OS 2 R/A calculates its generated power. Wherein I is OS The permeation current can be obtained by the data of a source meter, and R is an external resistor and can be obtained by correspondingThe value is read out, and A is the aperture area given by the aperture area of the focused ion beam.
The measurement results of the properties of the two-dimensional single-layer ion COF prepared in example 1 are shown in fig. 1 to 11.
FIG. 1 is a surface tension curve of a two-dimensional single-layer ion COF, and it can be seen that TFPP molecules are densely arranged at 10mN/m.
FIG. 2 is a graph showing the surface zeta potential of a two-dimensional monolayer COF in solutions of different pH, it can be seen that the zeta potential corresponds to a charge density of 4.4mC/m at pH=6 2 Provides necessary conditions for selectively transmitting chloride ions, and the non-ionic COF is-2.2 mC/m 2 Can be selective for sodium ions.
Whereas the charge density of the two-dimensional single-layer ion COF of comparative example 1 was-2.2 mC/m 2 I.e. the charge density is too small and cations are preferentially selected to pass through, so that under a NaCl salt difference system, the selected cations pass through to reduce the osmotic voltage and osmotic potential, which is unfavorable for the conversion output of osmotic energy.
Fig. 3 shows the contact angle of a two-dimensional single-layer ion COF, and the contact angle is smaller compared with a single-layer COF without positive surface charges, which indicates that the single-layer COF is more hydrophilic and is beneficial to high-flux passage of ions.
Fig. 4, 5 and 6 are representations of the optical, scanning electron microscope and transmission electron microscope of a two-dimensional single-layer ion COF, respectively, and it can be seen that the film can be prepared in a large area, is smooth and compact, has no residual nano particles, and can exist stably.
Fig. 7 is a frozen high resolution transmission electron microscope characterization of a two-dimensional single layer ion COF, and it can be seen that the pore size and corresponding diffraction fringes and pore size are 1.7nm, which can prove the presence of corresponding nanopores.
FIG. 8 is an atomic force microscope characterization of a two-dimensional monolayer ion COF, which can be seen to be 1nm thick.
Fig. 9 is an elemental image of a two-dimensional monolayer ion COF, which can be seen to include carbon and nitrogen atoms.
FIGS. 10, 11 and 12 are X-ray photoelectron spectroscopy, ultraviolet spectroscopy and Raman spectroscopy, respectively, showing that the charged COF has a distinct positive nitrogen peak compared to the monomeric and uncharged COFs, indicating successful material synthesis; the ultraviolet spectrum red shift shows that the material forms a large-area conjugated structure, which proves that the material is successfully synthesized; the formation of the imine bond and the elimination of the aldehyde group peak of the Raman spectrum show that the chemical reaction occurs, and the successful synthesis of the two-dimensional COF is realized.
Fig. 13 shows ion selectivity using different concentrations of potassium chloride solution, and it can be seen that the positive ion membrane selectively passes chloride ions.
FIG. 14 shows the maximum power density of 1062W/m obtained by testing the output power with sodium chloride solutions of different concentrations 2 Beyond the existing materials.
FIG. 15 is an I-V curve of an uncharged two-dimensional monolayer COF (COF film prepared in comparative example 1) tested using 0.5M/0.01M NaCl solution, and it can be seen that the permeation potential is small, which is disadvantageous for the conversion of permeation energy.
The pore size of the single-layer two-dimensional ion COF prepared in example 1 of the present invention was 1.7nm.
If tetra-aminophenylporphyrin and 1,1 '-bis (4-formylphenyl) -4,4' -bipyridine dichloride salt are adopted, the pore diameter is enlarged, the surface charge is reduced, the selectivity of the COF film is reduced, and the conversion of osmotic energy is not facilitated. Thus, the two-dimensional single-layer ion COF constructed by tetra-aldehyde phenyl porphyrin and ethidium bromide is selected as the osmotic energy conversion film, so that the osmotic energy output power can be improved.
Claims (8)
1. A two-dimensional single-layer ionic COF film is prepared by polymerizing 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin and ethidium bromide through Schiff base reaction to form imine covalent bond.
2. The two-dimensional single-layer ionic COF film according to claim 1, characterized in that: the thickness of the two-dimensional single-layer ion type COF film is 0.9-1.1 nm, and the aperture is 1.6-1.8 nm.
3. The method for preparing a two-dimensional single-layer ionic COF film according to claim 1 or 2, comprising the steps of:
dripping ethidium bromide and a catalyst into the uniformly spread 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin monolayer, and obtaining the two-dimensional single-layer ionic COF film through Schiff base reaction.
4. A method of preparation according to claim 3, characterized in that: the molar ratio of the 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin to the ethidium bromide is 1: 100-1: 200;
the catalyst is trifluoroacetic acid or glacial acetic acid;
the Schiff base reaction time is 24 hours.
5. The method according to claim 3 or 4, wherein: the 5,10,15, 20-tetrakis (4-aldehydephenyl) -21H, 23H-porphyrin monolayer was prepared according to the following procedure:
and (3) dripping the solution of the 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin into a drawing instrument through a microsyringe, and then sequentially performing solvent evaporation and sliding barrier compression to obtain the 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin monolayer.
6. The method of manufacturing according to claim 5, wherein: the solvent is evaporated for 20-40 min;
and compressing the slide barrier to ensure that the surface tension of the 5,10,15, 20-tetra (4-aldehyde benzene) -21H, 23H-porphyrin monomolecular layer is 9-11 mN/m.
7. Use of the two-dimensional single-layer ionic COF film according to claim 1 or 2 for osmotic energy conversion or as an osmotic energy conversion film.
8. Use of the two-dimensional single-layer ionic COF film according to claim 1 or 2 in salt differential energy power generation.
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| CN117638127B (en) * | 2024-01-26 | 2024-04-26 | 杭州德海艾科能源科技有限公司 | High-ion-selectivity mixed matrix porous diaphragm for vanadium battery and preparation method thereof |
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