CN113105628B - Imidazolyl porous organic polymer, preparation method thereof and application thereof in proton conducting material of fuel cell - Google Patents
Imidazolyl porous organic polymer, preparation method thereof and application thereof in proton conducting material of fuel cell Download PDFInfo
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Abstract
The invention provides an imidazolyl porous organic polymer, a preparation method thereof and application thereof in a proton conducting material of a fuel cell. The invention synthesizes imidazole-based POPs with high crystallinity, high specific surface area, porosity and high structural stability by using pyrene-4, 5,9, 10-tetrone, ammonium acetate and trimesic aldehyde as raw materials; the POPs containing high-density imidazole and pyrene groups are respectively subjected to sulfonation modification, phosphoric acid loading and phosphoric acid loading after sulfonation modification to obtain a series of functionalized imidazolyl POPs materials. The POPs material of the invention has good proton conductivity under wide temperature and humidity conditions, and has high use stability.
Description
Technical Field
The invention relates to an imidazolyl porous organic polymer, a preparation method thereof and application thereof in a proton conduction material of a fuel cell, belonging to the field of novel energy material in organic functional materials, namely a proton exchange membrane material of the fuel cell.
Background
In future social life of low carbon, the proton exchange membrane fuel cell has the characteristics of high conversion efficiency, environmental friendliness and the like, and is expected to become a powerful alternative scheme based on the conventional fossil fuel power technology. The proton exchange membrane is one of the core technologies of the fuel cell, and the proton conduction performance of the proton exchange membrane directly affects the final performance of the whole fuel cell. The material which has been commercialized in the technical field of proton exchange membranes at present is a perfluorosulfonic acid-based electrolyte polymer called Nafion; however, the application and popularization of the material are severely restricted by the complicated synthesis steps, the limited use temperature and humidity environment, the high cost and the like.
In recent years, Porous Organic Polymers (POPs) have received much attention for their preparation and application development due to their ease of synthesis and often their excellent physicochemical properties; however, its application to fuel cell proton exchange membranes is also limited by structural stability and proton conductivity. For example, chinese patent document CN111129557A discloses a phosphoric acid modified polybenzimidazole proton exchange membrane and a preparation method thereof, and the preparation method of the phosphoric acid modified polybenzimidazole proton exchange membrane comprises the following steps: s1, dissolving polybenzimidazole in an organic solvent for purification treatment to obtain a polybenzimidazole solution; s2, coating the polybenzimidazole solution on a flat plate to form a film, and drying; s3, carrying out acidic modification in a phosphoric acid steam atmosphere; and S4, curing at high temperature in vacuum to obtain the phosphoric acid modified polybenzimidazole proton exchange membrane. However, the preparation method of the invention is complicated, and the proton conductivity of the obtained proton exchange membrane is poor, and the structural stability is not involved. For another example, chinese patent document CN109786796A discloses a high temperature proton exchange membrane and a preparation method thereof; forming a cross-linked PBI membrane by reacting polybenzimidazole with a cross-linking agent; and carrying out quaternization reaction on the cross-linked PBI membrane and a quaternization substance to obtain the high-temperature proton exchange membrane. According to the invention, a specific quaternization substance (tertiary amine and/or imidazole derivative) is adopted to carry out quaternization reaction on the cross-linked membrane, and a specific quaternary ammonium group is introduced to form a quaternary ammonium cross-linked membrane, so that the mechanical property of the cross-linked membrane can be improved, and the proton conductivity and the phosphoric acid retention rate of the cross-linked membrane can also be improved; however, when used as a proton exchange membrane, the proton conductivity is still poor.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an imidazolyl porous organic polymer, a preparation method thereof and application thereof in a proton conducting material of a fuel cell. The invention synthesizes imidazole-based POPs with high crystallinity, high specific surface area, porosity and high structural stability by using pyrene-4, 5,9, 10-tetrone, ammonium acetate and trimesic aldehyde as raw materials; the POPs containing high-density imidazole and pyrene groups are respectively subjected to sulfonation modification, phosphoric acid loading and phosphoric acid loading after sulfonation modification to obtain a series of functionalized imidazolyl POPs materials. The POPs material of the invention has good proton conductivity under wide temperature and humidity conditions, and has high use stability.
The technical scheme of the invention is as follows:
an imidazolyl porous organic polymer, wherein the organic polymer is imidazolyl POPs (PyTFB-1 for short) and sulfonated and modified imidazolyl POPs (PyTFB-1-SO for short)3H) The proton carrier-loaded imidazolyl POPs or proton carrier-sulfonated modified imidazolyl POPs;
the imidazolyl POPs or the sulfonated modified imidazolyl POPs are two-dimensional porous polymers having structural units represented by the following formula (I);
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12Each independently selected from H or SO3H, said R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12The same or different.
Preferably according to the invention, the proton carrier is phosphoric acid or imidazole.
According to the invention, the specific surface area of the organic polymer is preferably 650-700m2Per g, the aperture is 1-16 nm; the organic polymer material has good crystallinity.
The preparation method of the imidazolyl POPs comprises the following steps: and (2) reacting pyrene-4, 5,9, 10-tetraone, ammonium acetate and trimesic aldehyde in an organic solvent A, and then washing and drying to obtain the imidazolyl POPs.
According to the invention, the pyrene-4, 5,9, 10-tetraone and trimesic aldehyde have the following structures:
according to the invention, the organic solvent A is preferably a mixed solvent of dioxane and mesitylene; the volume ratio of the dioxane to the mesitylene is 1:1-10, preferably 1: 3-5; the volume ratio of the amount of the pyrene-4, 5,9, 10-tetraone substance to the organic solvent A is 0.01-0.05 mol/L.
According to the invention, the mole ratio of the pyrene-4, 5,9, 10-tetraone, the ammonium acetate and the trimesic aldehyde is (1-2): 8-20): 1; preferably, the molar ratio of the pyrene-4, 5,9, 10-tetraketone to the ammonium acetate to the trimesic aldehyde is (1-2): (9-10): 1; further preferably, the molar ratio of the pyrene-4, 5,9, 10-tetraone, ammonium acetate and trimesic aldehyde is 1.5:9: 1.
According to the invention, the reaction temperature of pyrene-4, 5,9, 10-tetraone, ammonium acetate and trimesic aldehyde is preferably 130-180 ℃, and the reaction time is preferably 3-15 days; preferably, the reaction temperature is 140-160 ℃, and the reaction time is 4-6 days; most preferably, the reaction temperature is 160 ℃ and the reaction time is 5 days.
According to the invention, three freezing-air extraction-unfreezing circulation processes are required before the reaction of pyrene-4, 5,9, 10-tetraone, ammonium acetate and trimesic aldehyde, so that the reaction system is kept in a vacuum state, and the reaction is ensured to be carried out under the conditions of no oxygen and no water.
According to the invention, the reaction of pyrene-4, 5,9, 10-tetraone, ammonium acetate and trimesic aldehyde is preferably carried out in a thick-walled pressure-resistant tube or ampoule.
According to the invention, the washing is preferably carried out 2 to 3 times by sequentially using DMF, water, ethanol and dichloromethane, and then the Soxhlet extraction is carried out for 15 to 48 hours by using THF.
Preferably, according to the invention, the drying temperature is 80 to 120 ℃.
The preparation method of the sulfonated and modified imidazolyl POPs comprises the following steps: dispersing the prepared imidazolyl POPs in an organic solvent B, dropwise adding chlorosulfonic acid at the temperature of-20-10 ℃, heating for reaction after dropwise adding, and then washing and drying to obtain the sulfonated and modified imidazolyl POPs.
According to a preferred embodiment of the present invention, the organic solvent B is dichloromethane, N-methylpyrrolidone, mesitylene or tetrahydrofuran; the volume ratio of the mass of the imidazolyl POPs to the volume of the organic solvent B is 0.5g/L-3 g/L.
According to the invention, the mass ratio of the imidazolyl POPs to the chlorosulfonic acid is 1: 5-40; preferably, the mass ratio of the imidazolyl POPs to the chlorosulfonic acid is 1: 25-35.
According to the invention, the dropping temperature is preferably-5 to 5 ℃; the heating reaction temperature is 20-60 ℃, and the heating reaction time is 2 days to 10 days; preferably, the heating reaction temperature is 20-40 ℃, and the heating reaction time is 2 days to 4 days.
Preferably according to the invention, the washing is washing with water; the drying temperature is 60-120 ℃.
The preparation method of the proton carrier loaded imidazolyl POPs or proton carrier-sulfonated modified imidazolyl POPs comprises the following steps:
soaking the prepared imidazolyl POPs or the sulfonated modified imidazolyl POPs in 2-4mol/L proton carrier water solution for 12 hours, and then washing and drying to obtain the proton carrier loaded imidazolyl POPs or proton carrier-sulfonated modified imidazolyl POPs. The proton carrier is fixed in the POPs pore channels by an imidazolyl group and a sulfonic acid group through ionic bonds or hydrogen bonds.
Preferably according to the invention, the proton carrier is phosphoric acid or imidazole. When the proton carrier is phosphoric acid, the obtained proton carrier-supported imidazolyl POPs are abbreviated as H3PO4@ PyTFB-1, proton-carrying carrier-sulfonation-modified imidazolyl POPs abbreviated as H3PO4@PyTFB-1-SO3H. The phosphoric acid (H)3PO4) Has high proton concentration and low volatility (>158 deg.c), high mass mobility.
According to the invention, the soaking time is within the range of 0-12 h, the longer the soaking time is, the higher the proton conductivity is, and when the soaking time exceeds 12h, the proton conductivity is not increased any more; therefore, the soaking time was selected to be 12 hours.
The application of the imidazolyl porous organic polymer in a proton conducting material of a fuel cell is used as a proton exchange membrane in the fuel cell.
The invention has the following technical characteristics and beneficial effects:
1. the invention uses pyrene-4, 5,9, 10-tetraone, ammonium acetate and triphenylformaldehyde as raw materials to synthesize novel imidazolyl POPs containing high-density imidazole and pyrenyl groups in one step through a Debus-Radziszewski reaction; the proportions of pyrene-4, 5,9, 10-tetraone, ammonium acetate and trimesic aldehyde and the organic solvent A used are appropriate, and imidazole-based POPs having the structure and performance of the present invention cannot be obtained if the proportions or the kinds of the organic solvent A are not appropriate. At the same time, the reaction temperature also needs to be adapted, preferably in combination with freeze-pump-thaw cycling, to achieve the imidazolyl POPs of the present structures and properties.
The obtained imidazolyl POPs are sulfonated to obtain sulfonated modified imidazolyl POPs. The frameworks of the imidazolyl POPs and the sulfonated modified imidazolyl POPs have functional groups such as imidazolyl, sulfonic acid groups and the like, and the functionalized POPs have proton conductivity due to the existence of the groups. In addition, the existence of the imidazolyl group and the sulfonic group can enhance the adsorption performance of the POPs material on proton carriers, and the imidazolyl POPs material loaded with the proton carriers and sulfonated and modified and then loaded with the proton carriers can be further prepared, so that the proton conductivity of the material is enhanced.
2. The imidazolyl POPs prepared by the method are of porous structures, have large specific surface areas and regular pore channels, and have high crystallinity. The imidazolyl POPs prepared by the invention have high structural stability and excellent chemical stability, and can stably exist in various common organic solvents (N, N-dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, ethanol and the like), concentrated hydrochloric acid (6mol/L), concentrated alkali NaOH (6mol/L), concentrated phosphoric acid and boiling water. The imidazole groups with high density in the imidazole-based POPs prepared by the invention are excellent proton acceptors, and meanwhile, the imidazole groups can continuously load proton carriers to further improve the proton conductivity of the POPs. Thus, imidazole-based POPs have great potential as proton-conducting materials.
3. The imidazolyl porous organic polymer prepared by the method shows good proton conductivity under wide temperature and humidity conditions; the proton conductivity can reach 1.15 multiplied by 10-1S/cm, performance equivalent to that of the current commercial Nafion material (1 multiplied by 10)-1S/cm); the activation energy of proton conduction is lower, which indicates that the barrier of proton conduction of the material is smaller; the material has imidazole rigid skeleton, so that the material has higher structural stability and use stability compared with similar materials; is a new material potentially applicable to proton exchange membrane fuel cells.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of the PyTFB-1 synthesized in example 1 and simulated AA and AB stacking;
FIG. 2 is a Fourier infrared spectrum of PyTFB-1 synthesized in example 1 and starting material;
FIG. 3 is a nitrogen desorption isotherm for PyTFB-1 synthesized in example 1;
FIG. 4 is a graph showing the pore size distribution of PyTFB-1 synthesized in example 1;
FIG. 5 is a comparative powder X-ray diffraction pattern of PyTFB-1 synthesized in example 1 after solvent treatment;
FIG. 6 shows PyTFB-1-SO synthesized in example 23H Fourier infrared spectrum of PyTFB-1 synthesized in example 1;
FIG. 7 shows Nyquist plots (a) for PyTFB-1 synthesized in example 1 and H synthesized in example 3 at different temperatures3PO4Nyquist plots (b) of @ PyTFB-1 at different temperatures, PyTFB-1-SO synthesized in example 23Nyquist plot of H at different temperatures (c), H synthesized in example 43PO4@PyTFB-1-SO3Nyquist plot of H at different temperatures (d).
FIG. 8 shows PyTFB-1 synthesized in example 1 and H synthesized in example 33PO4@ PyTFB-1, PyTFB-1-SO synthesized in example 23H. H synthesized in example 43PO4@PyTFB-1-SO3Proton conduction of H is temperature dependent arrhenius.
FIG. 9 is H synthesized in example 43PO4@PyTFB-1-SO3H long term performance test plots.
Detailed Description
The invention will be further illustrated by means of specific embodiments in conjunction with the accompanying drawings, without limiting the scope of the invention thereto. The raw materials used in the examples are commercially available unless otherwise specified; the method is conventional unless otherwise specified, and the equipment is conventional unless otherwise specified.
Example 1
An imidazole-based porous organic polymer, PyTFB-1, was prepared as follows: pyrene-4, 5,9, 10-tetraone (0.06mmol), ammonium acetate (0.36mmol) and mesitylene (0.04mmol) were mixed and placed in an ampoule, followed by the addition of the solvents dioxane (0.6mL) and mesitylene (2.4mL) and mixed well. Freezing the reaction materials into solid at the temperature of liquid nitrogen and-78 ℃, vacuumizing to vacuum, then thawing until the reaction materials are liquid, repeating the steps for three times, keeping the ampoule bottle in a vacuum state after the three freezing-vacuumizing-thawing circulation processes, sealing the tube, then placing the ampoule bottle into a 160 ℃ oven for reaction for 5 days (the reactants are gradually heated to 160 ℃ from the low temperature after thawing for reaction), filtering to obtain the solid, washing the solid twice by sequentially using DMF, water, ethanol and dichloromethane, then transferring the solid to a Soxhlet extractor for washing by using THF for 48 hours, and drying at the temperature of 100 ℃ to obtain a brown PyTFB-1 product with the molar yield of 89%.
PyTFB-1 synthesized in this example and the starting materials pyrene-4, 5,9, 10-tetraone (PTO), ammonium acetate (NH)4The Fourier infrared spectra of OAc) and trimesic aldehyde (TFB) are shown in figure 2, and it can be seen that the target product is successfully prepared by the method.
Study of crystallinity of PyTFB-1:
the crystallinity of PyTFB-1 was examined by a powder diffractometer, and the powder X-ray diffraction pattern and the simulated powder X-ray diffraction patterns of AA deposition and AB deposition are shown in FIG. 1. XRD showed good peak pattern and very high peak intensity, indicating that PyTFB-1 has good crystallinity.
Investigation of PyTFB-1 porosity:
about 80mg of sample is weighed and activated for 12 hours at 120 ℃, and then a nitrogen 77K isothermal adsorption curve of the sample is tested by a gas adsorption instrument, wherein a nitrogen adsorption and desorption isothermal line is shown in figure 3, and a pore diameter distribution diagram is shown in figure 4. The results show that the synthesized PyTFB-1 has higher specific surface area (672 m)2,/g) and pore size (1.67 nm).
Chemical stability test of PyTFB-1:
PyTFB-1 is respectively soaked in DMF, DMSO, THF, ethanol, 6mol/L hydrochloric acid aqueous solution, 6mol/L NaOH aqueous solution and 6mol/L H3PO4The chemical stability of PyTFB-1 after soaking the solution in water and boiling water was examined by a powder diffractometer for 2 days, and the X-ray diffraction pattern is shown in FIG. 5. The results show that the peak of the PyTFB-1 powder is well retained after treatment with these harsh conditions, which shows their good structural stability.
Example 2
An imidazolyl porous organic polymer, i.e. sulfonated modified imidazolyl POPs (PyTFB-1-SO for short)3H) The preparation method comprises the following steps:
60mg of PyTFB-1 powder prepared in example 1 was dispersed in 60mL of dichloromethane, the temperature was lowered to 0 ℃ and 1.05mL of chlorosulfonic acid was added dropwise, after the addition was completed, the reaction was carried out at 30 ℃ for 72 hours, the mixture was filtered, and then the solid was washed thoroughly with water, and the resulting sample was dried under vacuum at 100 ℃ for 24 hours to obtain dry PyTFB-1-SO3H。
PyTFB-1-SO synthesized in this example3The Fourier infrared spectrum of H is shown in FIG. 6, and comparison with PyTFB-1 shows that sulfonated modified imidazolyl POPs were successfully prepared in this example.
Example 3
An imidazolyl porous organic polymer, namely, imidazolyl POPs (short for H) loaded with phosphoric acid3PO4The preparation method of @ PyTFB-1) is as follows:
60mg of PyTFB-1 prepared as in example 1 was soaked in 15mL of 3mol/L aqueous phosphoric acid solution for 12 hours, filtered, and then the solid was washed thoroughly with distilled water until the eluate reached pH 7, and the resulting sample was dried at 120 ℃ for 24 hours to obtain dried phosphoric acid-supported imidazole-based POPs.
Experiments show that the soaking time is within the range of 0-12 h, the longer the soaking time is, the higher the proton conductivity is, and when the soaking time exceeds 12h, the proton conductivity is not increased any more.
Example 4
An imidazolyl porous organic polymer, namely, loaded proton carrier-sulfonated modified imidazolyl POPs (abbreviated as H)3PO4@PyTFB-1-SO3H) The preparation method comprises the following steps:
60mg of the powder was takenPyTFB-1-SO prepared by the method of example 23H was soaked in 15mL of 3mol/L phosphoric acid aqueous solution for 12 hours, filtered, and then the solid was thoroughly washed with distilled water until the eluate reached pH 7, and then the resulting sample was dried at 120 ℃ for 24 hours to obtain dried proton-supported carrier-sulfonated modified imidazolyl POPs.
Experiments show that the soaking time is within the range of 0-12 h, the longer the soaking time is, the higher the proton conductivity is, and when the soaking time exceeds 12h, the proton conductivity is not increased any more.
Example 5
An imidazole-based porous organic polymer, PyTFB-1, was prepared as follows: pyrene-4, 5,9, 10-tetraone (0.04mmol), ammonium acetate (0.36mmol) and mesitylene (0.04mmol) were mixed and placed in an ampoule, followed by the addition of the solvents dioxane (0.6mL) and mesitylene (1.8mL) and mixed well. After three freeze-pump-thaw cycles as in example 1, the ampoule was kept under vacuum, the tube was sealed, and then placed in an oven at 140 ℃ for 6 days (the reaction was carried out by gradually raising the temperature of the reaction product from the low temperature after thawing to 140 ℃), the solid was obtained by filtration, washed twice with DMF, water, ethanol, and dichloromethane in sequence, then transferred to a soxhlet extractor and washed with THF for 48 hours, and dried at 100 ℃ to obtain brown PyTFB-1 product.
Example 6
An imidazole-based porous organic polymer, PyTFB-1, was prepared as follows: pyrene-4, 5,9, 10-tetraone (0.08mmol), ammonium acetate (0.4mmol) and mesitylene (0.04mmol) were mixed and placed in an ampoule, followed by the addition of the solvents dioxane (0.6mL) and mesitylene (3.0mL) and mixed well. After three freeze-pump-thaw cycles as in example 1, the ampoule was kept under vacuum, the tube was sealed, and then placed in an oven at 150 ℃ for 4 days (the reaction was carried out by gradually raising the temperature of the reaction product from the low temperature after thawing to 150 ℃), the solid was obtained by filtration, washed twice with DMF, water, ethanol, and dichloromethane in sequence, then transferred to a soxhlet extractor and washed with THF for 48 hours, and dried at 100 ℃ to obtain brown PyTFB-1 product.
Comparative example 1
Tooth-shape microphoneA method for preparing a azole-based porous organic polymer, PyTFB-1, was as follows: pyrene-4, 5,9, 10-tetraone (0.06mmol), ammonium acetate (0.36mmol) and mesitylene (0.04mmol) were mixed and placed in an ampoule, followed by the addition of the solvents dioxane (0.6mL) and mesitylene (2.4mL) and mixed well. After three freeze-pump-thaw cycles as in example 1, the ampoule was kept under vacuum, the tube was sealed, the reaction mixture was placed in an oven at 120 ℃ for 5 days (the reaction mixture was gradually warmed from room temperature to 120 ℃ for reaction), the solid was filtered, washed twice with DMF, water, ethanol, and dichloromethane, and then washed with THF in a Soxhlet extractor for 48 hours, and dried at 100 ℃ to obtain a brown PyTFB-1 product with a molar yield of 82%, which was tested to have a specific surface area of 489m2/g。
From this comparative example, it is understood that the reaction temperature is not suitable, and the specific surface area of the objective product to be obtained is greatly reduced.
Comparative example 2
An imidazole-based porous organic polymer, PyTFB-1, was prepared as follows: pyrene-4, 5,9, 10-tetraone (0.06mmol), ammonium acetate (0.36mmol) and mesitylene (0.04mmol) were mixed and placed in an ampoule, then the solvent mesitylene (3mL) was added and mixed well. After three freeze-pump-thaw cycles as in example 1, the ampoule was kept under vacuum, the tube was sealed, the reaction mixture was placed in an oven at 160 ℃ for 5 days (the reaction mixture was gradually warmed from room temperature to 160 ℃ for reaction), the solid was filtered, washed twice with DMF, ethanol and dichloromethane, washed with THF for 48 hours in a Soxhlet extractor, and dried at 100 ℃ to obtain brown PyTFB-1 product with a molar yield of 45% having a specific surface area of 263m2/g。
As can be seen from this comparative example, the choice of the solvent type has a significant influence on the yield of the desired product and also on the specific surface area.
Comparative example 3
An imidazole-based porous organic polymer, PyTFB-1, was prepared as follows: pyrene-4, 5,9, 10-tetraone (0.06mmol), ammonium acetate (0.36mmol) and mesitylene formaldehyde (0.04mmol) were mixed and placed in an ampoule, followed by addition of dioxane (0.6mL) as solventMesitylene (2.4mL) was mixed well. Vacuumizing once by adopting an air suction method, sealing a tube, then placing the tube into a drying oven at 160 ℃ for reaction for 5 days (the temperature of a reactant is gradually increased from room temperature to 160 ℃ for reaction), filtering to obtain a solid, washing the solid twice by sequentially using DMF (dimethyl formamide), water, ethanol and dichloromethane, then transferring the solid into a Soxhlet extractor for washing by using THF (tetrahydrofuran) for 48 hours, and drying the solid at 100 ℃ to obtain a brown PyTFB-1 product with the molar yield of 65 percent, wherein the specific surface area is tested to be 342m2/g。
According to the comparative example, the method of simply pumping air is adopted to pump vacuum once, so that the anaerobic and anhydrous condition of the reaction environment cannot be effectively maintained, and the yield and the specific surface area of the target product are greatly reduced.
Comparative example 4
An imidazole-based porous organic polymer, PyTFB-1, was prepared as follows: pyrene-4, 5,9, 10-tetraone (0.06mmol), ammonium acetate (0.36mmol) and mesitylene (0.04mmol) were mixed and placed in an ampoule, followed by the addition of solvents N-methylpyrrolidone (1.6mL) and mesitylene (0.8mL) and mixed well. After three freeze-pump-thaw cycles as in example 1, the ampoule was kept under vacuum, the tube was sealed, the reaction mixture was placed in an oven at 160 ℃ for 5 days (the reaction mixture was gradually heated from the low temperature after thawing to 160 ℃ for reaction), the solid was filtered, washed twice with DMF, water, ethanol and dichloromethane, and then transferred to a soxhlet extractor for 48 hours with THF, and dried at 100 ℃ to obtain brown PyTFB-1 product with a molar yield of 30%, which was tested to have a specific surface area of 101m2/g。
As can be seen from this comparative example, the choice of the solvent type has a significant influence on the yield of the desired product and also on the specific surface area.
Comparative example 5
An imidazole-based crystalline porous organic polymer, PyTFB-1, was prepared as follows: pyrene-4, 5,9, 10-tetraone (0.05mmol), ammonium acetate (0.36mmol) and mesitylene (0.05mmol) were mixed and placed in an ampoule, followed by the addition of the solvents dioxane (0.6mL) and mesitylene (2.4mL) and mixed well. After three freeze-pump-thaw cycles as in example 1, the ampoule was retainedSealing the tube in vacuum state, placing the tube in an oven at 160 ℃ for reaction for 5 days (the temperature of the reactant is gradually increased from the low temperature after unfreezing to 160 ℃ for reaction), filtering to obtain a solid, sequentially washing the solid twice with DMF (dimethyl formamide), water, ethanol and dichloromethane, then washing the solid for 48 hours with THF (tetrahydrofuran) in a Soxhlet extractor, and drying the solid at 100 ℃ to obtain a brown PyTFB-1 product with the molar yield of 64 percent and the specific surface area of 405m according to a test2/g。
From this comparative example, it can be seen that the raw material ratio has an important influence on the yield and specific surface area of the target product.
Test examples
Testing of proton conductive properties:
the ac impedance of the pressed sheets of the materials prepared in examples 1 to 4 was measured using an electrochemical workstation at a certain humidity and temperature, and the conductivity value was calculated using the formula σ ═ L/RA, where σ is the proton conductivity, L is the thickness of the sheet film, a is the area of the film, and R is the resistance.
Testing of proton conductivity as a function of temperature:
maintaining the humidity (98% RH) constant, changing the temperature at 30 deg.C, 40 deg.C, … deg.C, 80 deg.C, etc., and respectively measuring the AC impedance diagram, as shown in FIG. 7; the corresponding resistance values can be respectively read out through software fitting, and the proton conductivity can be calculated. From the results of fig. 7, it was found that the higher the temperature, the higher the proton conductivity.
As is clear from FIG. 7, H was synthesized at 80 ℃ and 98% RH3PO4@PyTFB-1-SO3H has high proton conductivity up to 1.15 × 10-1Proton conductivity of S/cm, which can even match that of commercial Nafion (-1X 10)-1S/cm). On the other hand, as can be seen from fig. 8, the proton conduction activation energies of the materials are all low, as low as 0.13eV, and none of them is higher than 0.4eV, which indicates that the proton conduction barriers of the materials are small.
For synthetic H at 80 ℃ and 98% RH3PO4@PyTFB-1-SO3H ac impedance test was performed for 48 hours, and proton conductivity was calculated. As shown in FIG. 9, synthesized H3PO4@PyTFB-1-SO3H can still maintain higher proton conductivity under the test time of 48 hours, which indicates that the material has high use stability.
Claims (12)
1. The imidazolyl porous organic polymer is characterized in that the organic polymer is imidazolyl POPs, sulfonated and modified imidazolyl POPs, proton carrier-loaded imidazolyl POPs or proton carrier-sulfonated and modified imidazolyl POPs;
the imidazolyl POPs or the sulfonated modified imidazolyl POPs are two-dimensional porous polymers having structural units represented by the following formula (I);
(I)
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12Each independently selected from H or SO3H, said R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12The same or different.
2. The imidazolyl porous organic polymer of claim 1, comprising one or more of the following conditions:
i. the proton carrier is phosphoric acid or imidazole;
ii. The specific surface area of the organic polymer is 650-700m2The pore diameter is 1-16 nm.
3. The method of preparing imidazolyl porous organic polymers according to claim 1, wherein the method of preparing imidazolyl POPs comprises the steps of: and (2) reacting pyrene-4, 5,9, 10-tetraone, ammonium acetate and trimesic aldehyde in an organic solvent A, and then washing and drying to obtain the imidazolyl POPs.
4. The method of preparing imidazolyl porous organic polymers according to claim 3, comprising one or more of the following conditions:
i. the organic solvent A is a mixed solvent of dioxane and mesitylene; the volume ratio of the dioxane to the mesitylene is 1: 1-10; the volume ratio of the amount of the pyrene-4, 5,9, 10-tetraone substance to the organic solvent A is 0.01-0.05 mol/L;
ii. The molar ratio of the pyrene-4, 5,9, 10-tetraketone to the ammonium acetate to the trimesic aldehyde is (1-2) to (8-20) to 1;
iii, the reaction temperature of the pyrene-4, 5,9, 10-tetraketone, the ammonium acetate and the trimesic aldehyde is 130-180 ℃, and the reaction time is 3-15 days;
before the reaction of iv, pyrene-4, 5,9, 10-tetraketone, ammonium acetate and triphenylformaldehyde, three times of freezing-air extraction-unfreezing circulation processes are needed to keep the reaction system in a vacuum state so as to ensure that the reaction is carried out under the oxygen-free and water-free conditions.
5. The method of preparing imidazolyl porous organic polymers according to claim 4, comprising one or more of the following conditions:
i. the volume ratio of the dioxane to the mesitylene is 1: 3-5;
ii. The molar ratio of the pyrene-4, 5,9, 10-tetraketone to the ammonium acetate to the trimesic aldehyde is (1-2) to (9-10) to 1;
iii, the reaction temperature of the pyrene-4, 5,9, 10-tetraketone, the ammonium acetate and the trimesic aldehyde is 140-160 ℃, and the reaction time is 4-6 days.
6. The method of preparing imidazolyl porous organic polymers according to claim 3, comprising one or more of the following conditions:
i. the reaction of pyrene-4, 5,9, 10-tetraketone, ammonium acetate and trimesic aldehyde is carried out in a thick-wall pressure-resistant tube or ampoule bottle;
ii. The washing is to wash the mixture for 2 to 3 times by sequentially using DMF, water, ethanol and dichloromethane, and then to perform Soxhlet extraction for 15 to 48 hours by using THF;
iii, the drying temperature is 80-120 ℃.
7. The method of preparing imidazolyl porous organic polymers of claim 1, wherein the method of preparing the sulfonate-modified imidazolyl POPs comprises the steps of: dispersing the imidazolyl POPs in an organic solvent B, dropwise adding chlorosulfonic acid at-20-10 ℃, carrying out heating reaction after dropwise adding is finished, and then washing and drying to obtain the sulfonated modified imidazolyl POPs.
8. The method of preparing imidazolyl porous organic polymers according to claim 7, comprising one or more of the following conditions:
i. the organic solvent B is dichloromethane, N-methyl pyrrolidone, mesitylene or tetrahydrofuran; the volume ratio of the mass of the imidazolyl POPs to the volume of the organic solvent B is 0.5g/L-3 g/L;
ii. The mass ratio of the imidazolyl POPs to the chlorosulfonic acid is 1: 5-40;
iii, the dropping temperature is-5-5 ℃; the heating reaction temperature is 20-60 ℃, and the heating reaction time is 2 days to 10 days;
iv, the washing is washing with water; the drying temperature is 60-120 ℃.
9. The method of preparing imidazolyl porous organic polymers according to claim 8, comprising one or more of the following conditions:
i. the mass ratio of the imidazolyl POPs to the chlorosulfonic acid is 1: 25-35;
ii. The heating reaction temperature is 20-40 ℃, and the heating reaction time is 2 days to 4 days.
10. The method for preparing imidazolyl porous organic polymers according to claim 1, wherein the proton carrier-supported imidazolyl POPs or proton carrier-sulfonation modified imidazolyl POPs are prepared by a method comprising the steps of:
soaking the imidazolyl POPs or the sulfonated modified imidazolyl POPs in a proton carrier aqueous solution of 2-4mol/L for 12 hours, and then washing and drying to obtain the proton carrier-loaded imidazolyl POPs or proton carrier-sulfonated modified imidazolyl POPs.
11. The method of claim 10, wherein the proton carrier is phosphoric acid or imidazole.
12. The use of the imidazolyl porous organic polymer of claim 1 in a proton conducting material for a fuel cell as a proton exchange membrane in a fuel cell.
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