CN114456339A - Covalent organic framework film with high content of ionic groups, preparation method and application thereof - Google Patents
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Abstract
The invention discloses a covalent organic framework film with high ionic group content, a preparation method and application thereof, wherein the covalent organic framework film is obtained by condensation polymerization of an amine monomer and an aldehyde monomer by a water phase-organic phase interface method, the raw materials comprise the aldehyde monomer activated by Bronsted acid in an organic phase and the amine monomer activated by Bronsted alkali in a water phase, and the amine monomer is an ionic amine monomer. According to the scheme, the interfacial reaction is accelerated through an activation technology, the ionic COF film can be synthesized in a short time by using the ionic amine monomer with low reactivity, the reaction efficiency is high, the product quality controllability is good, the crystallinity is good, the porosity is high, and the proton conductivity is excellent.
Description
Technical Field
The invention relates to the technical field of covalent organic framework membranes, in particular to a covalent organic framework membrane with high ionic group content, a preparation method and application thereof.
Background
Covalent Organic Frameworks (COFs) have the advantages of high surface area, adjustable pore size, predictable pore size, easy functionalization, excellent hydrothermal stability and the like, and have developed into a promising class of novel porous membrane materials. Ionic COF membranes have great potential for applications such as gradient energy conversion, ion conduction, ion separation and molecular sieving, because high content and monodispersed ionic groups can provide excellent ionic conductivity.
Due to the abundant monomer designability and mild reaction conditions, schiff-base reactions between amine monomers and aldehyde monomers are most commonly used for COF film manufacturing. Among the schiff base-reacted monomers, the ionic amine monomer is an essential constituent of the ionic COF film. With the benefit of simplicity and scalability, interfacial polymerization has evolved as a platform technology for COF film fabrication by confining the polymerization reaction between monomers to two immiscible phases at the interface. During interfacial polymerization, monomer reactivity directly controls the formation of the membrane structure. However, the interfacial polymerization technique for manufacturing non-ionic COF films is difficult to directly transfer to the ionic COF film manufacturing. In the previous reports, it takes 15 days to synthesize the ionic COF film by the interfacial polymerization method, and the prepared ionic COF film has poor crystallinity. This is because a monomer having a plurality of ionic groups generally exhibits lower reactivity due to strong electron-withdrawing and steric hindrance effects of the ionic groups. In addition, the proton of the ionic group or acid activator (catalyst) is readily reacted with-NH2Combine to form-NH3 +This inhibits the nucleophilic attack ability of the amine monomer.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a covalent organic framework film with high ionic group content, a preparation method and application thereof.
In order to achieve the above object, the embodiment of the present invention provides a covalent organic framework film with high content of ionic groups, which is obtained by performing condensation polymerization on an amine monomer and an aldehyde monomer by an aqueous phase-organic phase interface method, wherein the raw materials include an aldehyde monomer activated by a bronsted acid in an organic phase and an amine monomer activated by a bronsted base in an aqueous phase, and the amine monomer is an ionic amine monomer.
In one or more embodiments of the present invention, the covalent organic framework film with high ionic group content is obtained by condensation polymerization of an amine monomer and an aldehyde monomer by a water phase-organic phase interface method, the raw material includes a polybasic aldehyde monomer activated by bronsted acid in an organic phase and a polyamine monomer activated by bronsted base in a water phase, and the polyamine monomer is an ionic amine monomer.
In one or more embodiments of the present invention, at least some of the ionic amine monomers are amine monomers having ionic groups selected from at least-SO3H、-COOH、-PO3H2。
In one or more embodiments of the invention, the bronsted acid is a fatty acid that is insoluble or sparingly soluble in water.
In one or more embodiments of the present invention, the bronsted acid is selected from n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid.
In one or more embodiments of the invention, the bronsted base is a strong base and a weak acid salt.
In one or more embodiments of the present invention, the bronsted base is selected from sodium carbonate, sodium benzoate, sodium propionate, sodium acetate, sodium formate, potassium acetate.
In one or more embodiments of the invention, the amine monomer is selected from the group consisting of 2, 5-diaminobenzenesulfonic acid, 4' -diamino- [1,1' -biphenyl ] -3,3' -disulfonic acid, 3, 5-dihydrazinocarbonylbenzenesulfonic acid, 3, 5-dihydrazinocarbonylbenzoic acid, 3, 5-dihydrazinocarbonylphenylphosphonic acid.
In one or more embodiments of the present invention, the solvent of the organic phase is selected from mesitylene.
In one or more embodiments of the present invention, a method for preparing a high ionic group content covalent organic framework film comprises the steps of: preparing an aqueous solution comprising an amine monomer and a bronsted base; preparing an organic phase solution containing an aldehyde monomer and a Bronsted acid; slowly adding the organic phase solution into the water phase solution to form a two-phase system, and reacting to generate a membrane material; and (3) carrying out post-treatment on the membrane material to obtain the covalent organic framework membrane with high ionic group content.
In one or more embodiments of the invention, the use of a high ionic group content covalent organic framework membrane as described above in energy conversion, molecular sieving, ion conduction, ion separation.
In one or more embodiments of the present invention, a method for preparing a high ionic group content covalent organic framework film may include the steps of:
And 2, adding 30mL of the aqueous solution into a 100mL beaker, slowly adding 20mL of the organic phase solution above the aqueous solution along the wall of the beaker, and standing at room temperature for 24-48 hours.
And 3, taking out the ionic COF membrane at the interface, immersing the membrane in a Dimethylformamide (DMF) solution to wash away redundant monomers and solvents, immersing the membrane in a 0.5-3mol/L sulfuric acid solution for 24 hours, and washing the membrane to be neutral by using a large amount of water to obtain the ionic covalent organic framework membrane.
Further, the preparation method of the present invention, wherein:
in step 1, the bronsted acid is preferably a fatty acid immiscible with water, more preferably n-heptanoic acid, n-octanoic acid, n-nonanoic acid, or n-decanoic acid.
In step 1, the ratio of the bronsted acid to mesitylene may be any ratio, or may be pure bronsted acid, and is preferably (1: 1) to (4: 1).
In step 1, the preferred aldehyde monomer is 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde.
In step 1, the amine monomer may be any monomer having an ionic group (including-SO)3H、-COOH、-PO3H2Plasma group). The amine monomer is preferably selected from 2, 5-diaminobenzenesulfonic acid, 4 '-diamino- [1,1' -biphenyl]-3,3' -disulfonic acid, 3, 5-dihydrazinocarbonylbenzenesulfonic acid, 3, 5-dihydrazinocarbonylbenzoic acid, 3, 5-dihydrazinocarbonylphenylphosphonic acid.
In step 1, the bronsted base can be strong base and weak acid salt, preferably sodium carbonate, sodium benzoate, sodium propionate, sodium acetate, sodium formate and potassium acetate.
In step 1, the molar ratio of amine monomer activator to amine monomer is preferably (0.5-3.5): 1.
compared with the prior art, according to the covalent organic framework film with high ionic group content, the preparation method and the application thereof, the aldehyde monomer is dissolved in the organic phase by adopting a double-activation interface polymerization method, and then the Bronsted acid is added to activate the aldehyde monomer in the organic phase; the ionic amine monomer is dissolved in the aqueous phase, and then bronsted base is added to activate the ionic amine monomer in the aqueous phase. After activation, the two phases are mixed and the two monomers react at the interface to grow and assemble into an ionic COF film. Compared with the prior art, after activation, the interfacial reaction is accelerated, and the ionic COF film can be synthesized within 24-48 hours. The preparation method is simple and controllable, and the prepared ionic COF film has high crystallinity, high specific surface area, excellent stability, extremely high proton conductivity and application potential in the fields of lithium ion conduction, ion separation and molecular separation.
Drawings
FIG. 1 is TpBD (SO) prepared in example 13H)2Characterization of ionic covalent organic framework membranes. (a) TpBD (SO)3H)2SEM picture of cross section of ionic covalent organic framework membrane; (b) TpBD (SO)3H)2Digital photographs of ionic covalent organic framework films; (c) TpBD (SO)3H)2XRD diffraction profile of ionic covalent organic framework film; (d) TpBD (SO)3H)2Nitrogen adsorption and desorption curves of the ionic covalent organic framework membrane; (e) TpBD (SO)3H)2Chemical structural schematic of COFs.
FIG. 2 is TpBD (SO) prepared in example 13H)2Proton conductivity curve of ionic covalent organic frame membrane, test condition is 30-90 deg.C, 100% relative humidity.
FIG. 3 is TpPa-SO prepared in example 23Characterization of H-ionic covalent organic framework membranes. (a) TpPa-SO3A section SEM picture of an H-ion type covalent organic framework film; (b) TpPa-SO3Digital photographs of H-ion covalent organic framework membranes; (c) TpPa-SO3XRD diffraction profile of H ionic covalent organic framework film; (d) TpPa-SO3A nitrogen adsorption and desorption curve of the H-ion type covalent organic framework membrane; (e) TpPa-SO3Chemical structure schematic diagram of H COFs.
FIG. 4 is TpPa-SO prepared in example 23Proton conductivity curve of H-ion type covalent organic frame membrane, test condition is 30-90 deg.C, 100% relative humidity.
FIG. 5 shows TpBD (SO) prepared under different activator addition conditions in example 33H)2Ionic covalent organic frame film digital photo
Fig. 6 is (a) a schematic chemical structure, (b) an XRD characterization and (c) a digital photograph of the TpMbh-COOH ionic covalent organic framework film prepared in example 4.
FIG. 7 shows TpMbh-PO prepared in example 53H2Schematic of the chemical structure of ionic covalent organic framework films, (a) XRD characterization and (c) digital photographs.
FIG. 8 is TpBD (SO) prepared in comparative example 3 with addition of only amine monomer activator3H)2Characterization of ionic covalent organic framework membranes by (a) digital photograph, (b) SEM photograph, and (c) XRD.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the specific embodiments of the present invention, but it should be understood that the scope of the present invention is not limited by the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Example 1: high crystallinity TpBD (SO)3H)2Preparation of ionic covalent organic framework membranes
Adding 0.2mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene triformal into an organic phase mixed solution of 5mL of mesitylene and 15mL of n-octanoic acid, and oscillating and ultrasonically treating to obtain a clear solution; 0.3mmol of 4,4' -diamino- [1,1' -biphenyl ] -3,3' -disulfonic acid and 0.45mmol of sodium formate are added into 30mL of deionized water, and the mixture is subjected to ultrasonic treatment to obtain a water phase mixed solution. The aqueous solution was added to a 100mL beaker and then the organic phase mixture solution was slowly added to the aqueous solution along the wall of the beaker. The beaker was left to stand at room temperature for 24h, then the membrane located between the organic and aqueous phases was carefully removed with tweezers and immersed in a beaker containing 50mL of dimethylformamide solution, and the beaker was then placed in a shaker and shaken for 5h to wash off excess monomer and solvent. The membrane is taken out from the dimethylformamide and immersed in 1mol/L sulfuric acid for 24h for acidification, and then taken out and washed with deionized water for 3 times and immersed in the deionized water for preservation.
The performance test of the sample of this example is shown in FIGS. 1-2, wherein the SEM image of the film section in FIG. 1 is shown as a, and the digital photograph of the film is shown as b. The film XRD pattern (c) and the film BET pattern (d) demonstrate that the prepared COF film has high crystallinity and high porosity. The membrane proton conductivity is shown in FIG. 2, and it can be seen that TpBD (SO) was prepared3H)2The ionic covalent organic framework membrane has a proton conductivity of about 0.66S/cm at 90 deg.C and 100% relative humidity.
Example 2: high crystallinity TpPa-SO3Preparation of H-ion type covalent organic framework film
Adding 0.2mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene triformal into an organic phase mixed solution of 5mL of mesitylene and 15mL of n-octanoic acid, and oscillating and ultrasonically treating to obtain a clear solution; 0.3mmol of 2, 5-diaminobenzene sulfonic acid and 0.6mmol of potassium acetate are added into 30mL of deionized water, and the mixture is subjected to ultrasonic treatment to obtain a water-phase mixed solution. The aqueous solution was added to a 100mL beaker and then the organic phase mixture solution was slowly added to the aqueous solution along the wall of the beaker. The beaker was left to stand at room temperature for 24h, then the membrane located between the organic and aqueous phases was carefully removed with tweezers and immersed in a beaker containing 50mL of dimethylformamide solution, and the beaker was then placed in a shaker and shaken for 5h to wash off excess monomer and solvent. The membrane is taken out of the dimethylformamide and immersed in 0.5mol/L sulfuric acid for 24h for acidification, and then taken out and washed 3 times with deionized water and immersed in deionized water for preservation.
The performance test of the sample of this example is shown in FIGS. 3-4, wherein the SEM image of the membrane section is shown as a and the digital photograph of the membrane is shown as b in FIG. 3. The film XRD pattern (c) and the film BET pattern (d) demonstrate that the prepared COF film has high crystallinity and high porosity. The proton conductivity of the membrane is shown in FIG. 4, and it can be seen that TpPa-SO was produced3The proton conductivity of the H-ion type covalent organic framework membrane under the conditions of 90 ℃ and 100% relative humidity is about 0.2S/cm.
Example 3: TpBD (SO) prepared with addition of different activators3H)2Ionic covalent organic framework membranes
Adding 0.3mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene trimethyl aldehyde into an organic phase mixed solution containing 5mL of mesitylene and 15mL of n-nonanoic acid respectively, and oscillating and ultrasonically treating to obtain a clear solution; 0.45mmol of 4,4' -diamino- [1,1' -biphenyl ] -3,3' -disulfonic acid and 0.45mmol of sodium propionate were added to 30mL of deionized water, and an aqueous phase mixture was obtained by sonication. The aqueous solution was added to a 100mL beaker and then the organic phase mixture solution was slowly added to the aqueous solution along the wall of the beaker. The beaker was left to stand at room temperature for 24h, then the membrane located between the organic and aqueous phases was carefully removed with tweezers and immersed in a beaker containing 50mL of dimethylformamide solution, and the beaker was then placed in a shaker and shaken for 5h to wash off excess monomer and solvent. The membrane is taken out from the dimethylformamide and immersed in 3mol/L sulfuric acid for 24h for acidification, and then taken out and washed 3 times with deionized water and immersed in deionized water for preservation.
The digital photograph and thickness of each of the sample films 1-7 of this example are shown in FIG. 5. Meanwhile, XRD diffraction test and nitrogen adsorption and desorption test also show that each sample in the embodiment has high crystallinity and high porosity. The proton conductivities of ionic covalent organic framework membrane samples 1-7 prepared in this example were about 0.15S/cm, 0.25S/cm, 0.35S/cm, 0.48S/cm, 0.26S/cm, 0.21S/cm, and 0.19S/cm at 90 deg.C and 100% relative humidity, respectively.
Example 4 preparation of Ionic covalent organic framework Membrane of TpMbh-COOH
Adding 0.04mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene triformal into an organic phase mixed solution containing 5mL of mesitylene and 15mL of n-decanoic acid respectively, and oscillating and ultrasonically treating to obtain a clear solution; 0.06mmol of 3, 5-dihydrazinocarbonylbenzoic acid and 0.03mmol of sodium benzoate were added to 30mL of deionized water, and the mixture was subjected to ultrasonic treatment to obtain a water-phase mixed solution. The aqueous solution was added to a 100mL beaker and then the organic phase mixture solution was slowly added to the aqueous solution along the wall of the beaker. The beaker was left to stand at room temperature for 24h, then the membrane located between the organic and aqueous phases was carefully removed with tweezers and immersed in a beaker containing 50mL of dimethylformamide solution, and the beaker was then placed in a shaker and shaken for 5h to wash off excess monomer and solvent. The membrane is taken out of the dimethylformamide and immersed in 2mol/L sulfuric acid for 24h for acidification, and then taken out and washed with deionized water for 3 times and immersed in the deionized water for preservation.
Example 5TpMbh-PO3H2Preparation of ionic covalent organic framework membranes
Respectively adding 0.08mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene triformal into an organic phase mixed solution containing 5mL of mesitylene and 15mL of n-octanoic acid, and oscillating and ultrasonically treating to obtain a clear solution; 0.18mmol of 3, 5-dihydrazinocarbonylphenylphosphonic acid and 0.6mmol of sodium carbonate are added to 30mL of deionized water, and the mixture is subjected to ultrasonic treatment to obtain a water-phase mixed solution. The aqueous solution was added to a 100mL beaker and then the organic phase mixture solution was slowly added to the aqueous solution along the walls of the beaker. The beaker was left to stand at room temperature for 24h, then the membrane located between the organic and aqueous phases was carefully removed with tweezers and immersed in a beaker containing 50mL of dimethylformamide solution, and the beaker was then placed in a shaker and shaken for 5h to wash off excess monomer and solvent. The membrane is taken out of the dimethylformamide and immersed in 1.5mol/L sulfuric acid for 24h for acidification, and then taken out and washed 3 times with deionized water and immersed in deionized water for preservation.
In summary, the double-activation interfacial polymerization method provided by the present invention can provide a method for preparing an ionic COF film. The method has better universality, and the prepared COF film has high crystallinity and high specific surface area. Wherein TpBD (SO)3H)2The proton conductivity of the ionic covalent organic framework membrane under the conditions of 90 ℃ and 100% relative humidity reaches 0.66S/cm.
Comparative example 1: preparation of TpBD (SO) without activator addition3H)2Ionic covalent organic framework membranes
Adding 0.2mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene trimethyl aldehyde into an organic phase of 20mL of mesitylene, and oscillating and ultrasonically treating to obtain a clear solution; 0.3mmol of 4,4' -diamino- [1,1' -biphenyl ] -3,3' -disulfonic acid was added to 30mL of deionized water, and the mixture was subjected to ultrasonic treatment to obtain an aqueous mixed solution. The aqueous solution was added to a 100mL beaker and then the organic phase mixture solution was slowly added to the aqueous solution along the wall of the beaker. The beaker was allowed to stand at room temperature for 24 h. No film could be obtained under such conditions without activator addition.
Comparative example 2: TpBD (SO) attempted with aldehyde monomer activator alone3H)2Ionic covalent organic framework membranes
Adding 0.2mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene triformal into a mixed organic phase solution of 5mL of mesitylene and 15mL of n-octanoic acid, and oscillating and ultrasonically treating to obtain a clear solution; 0.3mmol of 4,4' -diamino- [1,1' -biphenyl ] -3,3' -disulfonic acid is added into 30mL of deionized water, and the mixture is subjected to ultrasonic treatment to obtain a water-phase mixed solution. The aqueous solution was added to a 100mL beaker and then the organic phase mixture solution was slowly added to the aqueous solution along the wall of the beaker. The beaker was allowed to stand at room temperature for 24 h. A film cannot be obtained with the addition of the aldehyde monomer activator alone.
Comparative example 3: preparation of TpBD (SO) with the sole addition of an amine monomer activator3H)2Ionic covalent organic framework membranes
Adding 0.2mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene trimethyl aldehyde into 20mL of mesitylene organic phase, and oscillating and ultrasonically treating to obtain a clear solution; adding 0.3mmol of 4,4 '-diamino- [1,1' -biphenyl]Adding 3,3' -disulfonic acid and 0.45mmol of sodium formate into 30mL of deionized water, and carrying out ultrasonic treatment to obtain a water-phase mixed solution. The aqueous solution was added to a 100mL beaker and then the organic phase mixture solution was slowly added to the aqueous solution along the wall of the beaker. The beaker was left to stand at room temperature for 24h, then the membrane located between the organic and aqueous phases was carefully removed with tweezers and immersed in a beaker containing 50mL of dimethylformamide solution, and the beaker was then placed in a shaker and shaken for 5h to wash off excess monomer and solvent. The membrane is taken out from the dimethylformamide and immersed in 1mol/L sulfuric acid for 24h for acidification, and then taken out and washed with deionized water for 3 times and immersed in the deionized water for preservation. TpBD (SO) prepared with the addition of an amine monomer activator alone, as shown in FIG. 83H)2The ionic covalent organic framework film has low crystallinity and proton conductivity of 0.22S cm-1Lower than TpBD (SO) prepared under dual activation conditions3H)2Ionic covalent organic framework membranes.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A covalent organic framework membrane with high ionic group content is obtained by condensation polymerization of an amine monomer and an aldehyde monomer by a water phase-organic phase interface method, the raw materials comprise a polybasic aldehyde monomer with Bronsted acid activated in an organic phase and a polybasic amine monomer with Bronsted alkali activated in a water phase, and the amine monomer is an ionic amine monomer.
2. The covalent organic framework membrane of claim 1 wherein at least a portion of the ionic amine monomers are amine monomers with ionic groups selected from at least-SO3H、-COOH、-PO3H2。
3. The covalent organic framework membrane of high ionic group content of claim 1 wherein the bronsted acid is a fatty acid that is insoluble or sparingly soluble in water.
4. The covalent organic framework membrane of high ionic group content of claim 3 wherein the Bronsted acid is selected from n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic acid.
5. The high ionic group content covalent organic framework membrane of claim 1 wherein the bronsted base is a strong base and a weak acid salt.
6. The covalent organic framework film of high ionic group content of claim 5 wherein the Bronsted base is selected from sodium carbonate, sodium benzoate, sodium propionate, sodium acetate, sodium formate, potassium acetate.
7. The covalent organic framework membrane of high ionic group content of claim 2 wherein the amine monomer is selected from the group consisting of 2, 5-diaminobenzenesulfonic acid, 4' -diamino- [1,1' -biphenyl ] -3,3' -disulfonic acid, 3, 5-dihydrazinocarbonylbenzenesulfonic acid, 3, 5-dihydrazinocarbonylbenzoic acid, 3, 5-dihydrazinocarbonylphenylphosphonic acid.
8. The covalent organic framework membrane of high ionic group content of claim 1 wherein the solvent of the organic phase is selected from mesitylene.
9. The method for preparing a covalent organic framework membrane with high ionic group content according to claim 1, comprising the following steps:
preparing an aqueous solution comprising an amine monomer and a bronsted base;
preparing an organic phase solution containing an aldehyde monomer and a Bronsted acid;
slowly adding the organic phase solution into the water phase solution to form a two-phase system, and reacting to generate a membrane material;
and (3) carrying out post-treatment on the membrane material to obtain the covalent organic framework membrane with high ionic group content.
10. Use of the high ionic group content covalent organic framework membrane according to any of claims 1 to 8 for energy conversion, molecular sieving, ion conduction, ion separation.
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Cited By (2)
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| CN115521425A (en) * | 2022-09-02 | 2022-12-27 | 佛山仙湖实验室 | Covalent organic framework proton-conducting electrolyte material and preparation method and application thereof |
| CN116785952A (en) * | 2023-08-22 | 2023-09-22 | 天津大学浙江研究院 | Covalent organic framework nanofiltration membrane and preparation method thereof |
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