CN109867762B - Medium-high temperature proton conducting material with nitrogen-containing microporous structure and preparation method thereof - Google Patents
Medium-high temperature proton conducting material with nitrogen-containing microporous structure and preparation method thereof Download PDFInfo
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- CN109867762B CN109867762B CN201910064422.8A CN201910064422A CN109867762B CN 109867762 B CN109867762 B CN 109867762B CN 201910064422 A CN201910064422 A CN 201910064422A CN 109867762 B CN109867762 B CN 109867762B
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Abstract
The material prepared by the invention has nitrogen-containing alkaline sites for stabilizing phosphoric acid adsorbed in pore channels, non-volatile phosphoric acid is doped into a porous framework to form a continuous hydrogen bond network, so that the proton conductivity of the material is improved, the stability is good, the phosphoric acid cannot be lost in the main framework due to heating or in a humid environment, and the proton conductivity of the material at 120 ℃ can reach 1.26 × 10‑3S·cm‑1。
Description
Technical Field
The invention belongs to the field of preparation methods of proton conducting materials, and particularly relates to a medium-high temperature proton conducting material with a nitrogen-containing microporous structure and a preparation method thereof.
Background
The proton exchange membrane fuel cell has the advantages of low working temperature, quick start, high specific power, simple structure, convenient operation and the like, and is the preferred energy of future mobile energy storage equipment. The proton exchange membrane provides a channel for the migration and transportation of protons inside the cell, so that the protons pass through the membrane from the anode to the cathode, and form a loop with the electron transfer of an external circuit to provide current to the outside, and therefore the performance of the proton exchange membrane plays a decisive role in the performance of the fuel cell.
The Proton Exchange Membrane (PEMFC) most commonly used so far is still Nafion membrane of dupont in the united states, which has the advantages of high proton conductivity and good chemical stability, but Nafion series membrane still has the following disadvantages: (1) the preparation is difficult, the cost is high, the synthesis and sulfonation of the perfluoro-material are very difficult, and the hydrolysis and sulfonation in the film forming process can easily denature and degrade the polymer, so that the film forming is difficult, and the cost is high; (2) the requirements on temperature and water content are high, the optimal working temperature of the Nafion series membrane is 70-90 ℃, the water content of the Nafion series membrane is rapidly reduced when the temperature is exceeded, and the conductivity is rapidly reduced, so that the aims of accelerating the electrode reaction speed and overcoming catalyst poisoning by increasing the working temperature are difficult to achieve; (3) some hydrocarbons, such as methanol and the like, have high permeability, and therefore Nafion series membranes are not suitable for use as proton exchange membranes for Direct Methanol Fuel Cells (DMFC). Therefore, it is of great significance to search for a novel proton conductive material with low cost and high performance.
Disclosure of Invention
The invention aims to provide a medium-high temperature proton conducting material with a nitrogen-containing microporous structure and a preparation method thereof, and aims to solve the problems that the existing proton conducting material is high in production cost, complex in preparation process and greatly reduced in proton conductivity under the conditions of high temperature and low humidity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a medium-high temperature proton conducting material with a nitrogen-containing micropore structure has a structural formula shown as a formula (I):
a preparation method of a medium-high temperature proton conducting material with a nitrogen-containing microporous structure comprises the following steps:
the method comprises the following steps: putting 2,4, 6-triaminopyrimidine and 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde into a reaction container, adding a reaction solvent and a catalyst, and reacting for 5-6 days at 100-130 ℃ to obtain a mixed solution;
step two: respectively washing the mixed solution obtained in the step one with N, N-dimethylformamide and a methanol solution to remove soluble organic matters, performing Soxhlet extraction on the product with methanol for 1-2 days, and drying to obtain a powder material with a nitrogen-containing microporous structure;
step three: and (3) soaking the powder material obtained in the step two in concentrated phosphoric acid for 3-5 days, then further filtering to obtain a solid dispersion loaded with phosphoric acid, and drying the solid dispersion to obtain the medium-high temperature proton conducting material with the nitrogen-containing microporous structure.
Furthermore, the molar ratio of the 2,4, 6-triaminopyrimidine to the 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde is 1: 1.
Further, the reaction solvent is dichlorobenzene, butanol, N-Dimethylformamide (DMF), 1, 4-dioxane or 1,3, 5-trimethylbenzene.
Further, the catalyst is acetic acid.
Further, the concentration of the acetic acid was 6 mol/L.
Further, the volume ratio of the catalyst to the reaction solvent was 2: 5.
Further, the drying in the second step is specifically as follows: drying for 12 hours in a vacuum drier at the temperature of 60-100 ℃.
Further, the drying in the third step is specifically as follows: drying for 12 hours in a vacuum drier at 100-150 ℃.
Compared with the prior art, the invention has the following beneficial technical effects:
the medium-high temperature proton conducting material prepared by the invention has nitrogen-containing alkaline sites for stabilizing phosphoric acid adsorbed in pore channels, non-volatile phosphoric acid is doped into a porous framework to form a continuous hydrogen bond network, the proton conducting property of the material is improved, the material has good stability, the phosphoric acid cannot be lost in the main framework due to heating or in a humid environment, and the proton conductivity of the material at 120 ℃ can reach 1.26 × 10-3S·cm-1。
Drawings
FIG. 1 is a powder diffraction (PXRD) pattern of a medium-high temperature proton-conducting material having a nitrogen-containing microporous structure prepared in example 1;
FIG. 2 shows N of the middle-high temperature proton-conducting material having nitrogen-containing microporous structure prepared in example 12An adsorption-desorption isotherm diagram, wherein a square connecting line is an adsorption curve and a circular connecting line is a desorption curve;
FIG. 3 is a scanning electron microscope image of the medium-high temperature proton-conducting material having a nitrogen-containing microporous structure prepared in example 1;
FIG. 4 is a pore size distribution diagram of the medium-high temperature proton-conducting material having a nitrogen-containing microporous structure prepared in example 1;
fig. 5 is a proton conduction impedance spectrum of the middle-high temperature proton-conducting material having a nitrogen-containing microporous structure prepared in example 1.
Detailed Description
Embodiments of the invention are described in further detail below:
the invention provides a medium-high temperature proton conducting material with a nitrogen-containing microporous structure, which has a structural formula shown as a formula (I):
the invention also provides a preparation method of the medium-high temperature proton conducting material with the nitrogen-containing microporous structure, which comprises the following steps:
the method comprises the following steps: putting 2,4, 6-triaminopyrimidine and 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde into a reaction container, adding a reaction solvent and a catalyst, and reacting for 5-6 days at 100-130 ℃ to obtain a mixed solution;
step two: and (3) washing the mixed solution obtained in the step one with DMF (dimethyl formamide) and methanol solution respectively to remove soluble organic matters, performing Soxhlet extraction on the product with methanol for 1-2 days, and drying in a vacuum drier at 60-100 ℃ for 12 hours to obtain the powder material with the nitrogen-containing microporous structure.
Step three: and (3) soaking the powder material obtained in the step two in concentrated phosphoric acid for 3-5 days, further filtering to obtain a solid dispersion loaded with phosphoric acid, and drying the solid dispersion in a vacuum dryer at 100-150 ℃ for 12 hours to obtain the medium-high temperature proton conducting material with the nitrogen-containing microporous structure.
According to the invention, firstly, monomer 2,4, 6-triaminopyrimidine and 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid (TFP) are added into a reaction container, then a reaction solvent and a catalyst are added into the reaction container, and the mixture is reacted for 5 to 6 days at the temperature of 100 ℃ and 130 ℃ to obtain a mixed solution; the mol ratio of the 2,4, 6-triaminopyrimidine to the 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde is preferably 1: 1.
The amount of the reaction solvent is not particularly limited, and it is sufficient to dissolve the monomers 2,4, 6-triaminopyrimidine and 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid (TFP), and the reaction solvent is preferably dichlorobenzene, butanol, N-dimethylformamide, 1, 4-dioxane, or 1,3, 5-trimethylbenzene
The catalyst is preferably 6 mol/L of acetic acid, and the addition amount of the catalyst is 40% of the volume of the reaction solvent.
According to the invention, the obtained mixed solution is respectively washed by N, N-Dimethylformamide (DMF) and methanol solution to remove soluble organic matters, and the product is dried in vacuum at 60-100 ℃ for 12 hours to obtain the powder material with the nitrogen-containing microporous structure.
According to the invention, a powder material is soaked in phosphoric acid for 3-5 days, then methanol is used for diluting and washing the mixed solution, solid powder loaded with phosphoric acid is obtained by further filtering, and the powder is dried in vacuum at 100-150 ℃ for 12 hours, so that the medium-high temperature proton conducting material with a nitrogen-containing microporous structure is obtained.
The present invention is described in further detail below with reference to examples:
example 1
Step one, adding 1mmol of monomer 2,4, 6-triaminopyrimidine and 1mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene Triformol (TFP) into a reaction kettle, then adding 10m L of 1, 4-dioxane solvent, stirring uniformly, adding 4m L of 6 mol/L of acetic acid as a catalyst, and reacting for 6 days at 100 ℃ to obtain a mixed solution;
step two: washing the mixed solution obtained in the step one with N, N-Dimethylformamide (DMF) solution and methanol solution respectively, soxhlet extracting the filtered powder with methanol for 2 days, and vacuum drying the product at 100 ℃ for 12 hours to obtain the powdery material with the nitrogen-containing microporous structure.
Step three: and (3) soaking the powder material obtained in the step two in concentrated phosphoric acid for 5 days, further filtering to obtain a solid dispersion loaded with phosphoric acid, and drying the solid dispersion in a vacuum dryer at 150 ℃ for 12 hours to obtain the medium-high temperature proton conducting material with the nitrogen-containing microporous structure.
FIG. 1 is a powder diffraction (PXRD) pattern of a medium-high temperature proton-conducting material having a nitrogen-containing microporous structure prepared in example 1; it can be seen from the figure that the material has good crystallinity.
FIG. 2 shows the medium-high temperature proton conductive material having nitrogen-containing microporous structure prepared in example 1N of material2Adsorption-removal of attached figures; as can be seen from FIG. 2, by N2The BET specific surface area of the obtained medium-high temperature proton conduction material reaches 914.6m2/g。
FIG. 3 is a scanning electron microscope image of the medium-high temperature proton-conducting material having a nitrogen-containing microporous structure prepared in example 1;
FIG. 4 is a pore size distribution diagram of the medium-high temperature proton-conducting material having a microporous structure prepared in example 1; the average pore diameter is 0.6nm, as can be seen from the figure.
FIG. 5 is a proton conductivity impedance spectrum of the medium-high temperature proton-conducting material having a microporous structure prepared in example 1, wherein the proton conductivity of the material at 120 ℃ is 1.26 × 10-3S·cm-1。
Example 2
Step one, adding 1mmol of monomer 2,4, 6-triaminopyrimidine and 1mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene Triformal (TFP) into a reaction kettle, then adding 10m L of 1,3, 5-trimethylbenzene solvent, stirring uniformly, adding 4m L of 6 mol/L of acetic acid as a catalyst, and reacting for 5 days at 130 ℃ to obtain a mixed solution;
step two: washing the mixed solution obtained in the step one with N, N-Dimethylformamide (DMF) solution and methanol solution respectively, soxhlet extracting the filtered powder with methanol for 1 day, and vacuum drying the product at 60 ℃ for 12 hours to obtain the powdery material with the nitrogen-containing microporous structure.
Step three: and (3) soaking the powder material obtained in the step two in concentrated phosphoric acid for 4 days, further filtering to obtain a solid dispersion loaded with phosphoric acid, and drying the solid dispersion in a vacuum dryer at 100 ℃ for 12 hours to obtain the medium-high temperature proton conducting material with the nitrogen-containing microporous structure.
The solvent of this example may also be dichlorobenzene.
Example 3
Step one, adding 1mmol of monomer 2,4, 6-triaminopyrimidine and 1mmol of 2,4, 6-trihydroxy-1, 3, 5-benzene Triformal (TFP) into a reaction kettle, then adding 10m L of N, N-dimethylformamide solvent, stirring uniformly, adding 4m L of 6 mol/L of acetic acid as a catalyst, and reacting at 120 ℃ for 6 days to obtain a mixed solution;
step two: washing the mixed solution obtained in the step one with N, N-Dimethylformamide (DMF) solution and methanol solution respectively, soxhlet extracting the filtered powder with methanol for 2 days, and vacuum drying the product at 80 ℃ for 12 hours to obtain the powdery material with the nitrogen-containing microporous structure.
Step three: and (3) soaking the powder material obtained in the step two in concentrated phosphoric acid for 3 days, further filtering to obtain a solid dispersion loaded with phosphoric acid, and drying the solid dispersion in a vacuum dryer at 130 ℃ for 12 hours to obtain the medium-high temperature proton conducting material with the nitrogen-containing microporous structure.
The solvent of this example may also be butanol.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (9)
1. A medium-high temperature proton conducting material with a nitrogen-containing micropore structure is characterized in that the structural formula is shown as the formula (I):
the preparation method comprises the following steps:
the method comprises the following steps: putting 2,4, 6-triaminopyrimidine and 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde into a reaction container, adding a reaction solvent and a catalyst, and reacting for 5-6 days at 100-130 ℃ to obtain a mixed solution;
step two: respectively washing the mixed solution obtained in the step one with N, N-dimethylformamide and a methanol solution to remove soluble organic matters, performing Soxhlet extraction on the product with methanol for 1-2 days, and drying to obtain a powder material with a nitrogen-containing microporous structure;
step three: and (3) soaking the powder material obtained in the step two in concentrated phosphoric acid for 3-5 days, then further filtering to obtain a solid dispersion loaded with phosphoric acid, and drying the solid dispersion to obtain the medium-high temperature proton conducting material with the nitrogen-containing microporous structure.
2. A method for preparing the medium-high temperature proton-conducting material having a nitrogen-containing microporous structure according to claim 1, comprising the steps of:
the method comprises the following steps: putting 2,4, 6-triaminopyrimidine and 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde into a reaction container, adding a reaction solvent and a catalyst, and reacting for 5-6 days at 100-130 ℃ to obtain a mixed solution;
step two: respectively washing the mixed solution obtained in the step one with N, N-dimethylformamide and a methanol solution to remove soluble organic matters, performing Soxhlet extraction on the product with methanol for 1-2 days, and drying to obtain a powder material with a nitrogen-containing microporous structure;
step three: and (3) soaking the powder material obtained in the step two in concentrated phosphoric acid for 3-5 days, then further filtering to obtain a solid dispersion loaded with phosphoric acid, and drying the solid dispersion to obtain the medium-high temperature proton conducting material with the nitrogen-containing microporous structure.
3. The method for preparing the middle-high temperature proton conducting material with the nitrogen-containing microporous structure according to claim 2, wherein the molar ratio of the 2,4, 6-triaminopyrimidine to the 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde is 1: 1.
4. The method according to claim 2, wherein the reaction solvent is dichlorobenzene, butanol, N-Dimethylformamide (DMF), 1, 4-dioxane or 1,3, 5-trimethylbenzene.
5. The method according to claim 2, wherein the catalyst is acetic acid.
6. The method for preparing a medium-high temperature proton-conducting material having a nitrogen-containing microporous structure according to claim 5, wherein the concentration of the acetic acid is 6 mol/L.
7. The method according to claim 5, wherein the volume ratio of the catalyst to the reaction solvent is 2: 5.
8. The method for preparing the medium-high temperature proton conducting material with the nitrogen-containing microporous structure according to claim 2, wherein the drying in the second step is specifically: drying for 12 hours in a vacuum drier at the temperature of 60-100 ℃.
9. The method for preparing the medium-high temperature proton conducting material with the nitrogen-containing microporous structure according to claim 2, wherein the drying in the third step is specifically: drying for 12 hours in a vacuum drier at 100-150 ℃.
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