CN108084452B - Metal-organic framework type proton conductor material applicable under high-temperature and low-humidity conditions and preparation method thereof - Google Patents
Metal-organic framework type proton conductor material applicable under high-temperature and low-humidity conditions and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a metal-organic framework type proton conductor material applicable under the conditions of high temperature and low humidity and a preparation method thereof, wherein the preparation method comprises the following specific steps: 1) according to molar ratio, metal salt: phosphonic acid-azacyclic aromatic ligands: 0.1-10% of organic amine: 1: 0.2-5 of weighing raw materials; 2) adding raw material metal salt, phosphonic acid-nitrogen heterocyclic aromatic ligand and organic amine into a solvent, stirring at room temperature to obtain uniform sol, transferring the sol into a hydrothermal reaction kettle lined with polytetrafluoroethylene, placing the hydrothermal reaction kettle in a constant-temperature oven, carrying out hydrothermal reaction under the autogenous pressure of the solution, cooling reaction liquid to room temperature after the reaction is finished, precipitating crystals, and then filtering, washing and drying to obtain the catalyst. The anhydrous conductivity of the organic proton conductor material at 140 ℃ and RH 10% is 0.052-0.071S/cm, and the ion exchange capacity is 0.54-0.74 mg/mol.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and relates to a metal-organic framework type proton conductor material applicable under the conditions of high temperature and low humidity and a preparation method thereof.
Background
In recent years, with the rapid increase of the demand of people for clean energy materials, the synthesis and application research of metal-organic framework type proton conductor materials has become a hot spot for the development of new conductive materials. The micropore self-assembly material effectively combines the advantages of conductive materials and metal organic framework Materials (MOFs), not only can visually design the framework of the solid conductive material, but also can better realize proton transfer. Based on the above advantages, more and more researchers are focusing on a novel metal-organic framework type proton conductive material and investigating the possibility of applying it to a fuel cell.
Metal-organic framework type proton conductor materials can be broadly classified into two types: the first type is a metal organic framework conductive material with water molecules participating in proton conduction, and is generally used in a system with lower temperature (20-100 ℃) and certain humidity; the second type is an anhydrous proton conducting metal organic framework conducting material, which is usually used at high temperature (100-. The metal-organic framework type proton conductor materials reported so far generally have high proton conductivity under low-temperature, high-humidity conditions, and poor conductivity under high-temperature, low-humidity conditions. However, in industrial production, materials having high conductivity in both systems are currently the most demanded in practical applications.
In the preparation process of the metal-organic framework type proton conductor material, the design and synthesis of the ligand are very important in order to achieve excellent stability and conductivity. The common ligands have three main groups, carboxylic acids, nitrogen heterocycles and phosphonic acids, and each has the advantages and disadvantages: the carboxylic acid coordination polymer is easy to design and construct a porous topological structure and a high specific surface, but the water stability and the stability in the air are poor; the nitrogen heterocyclic coordination polymer has very good thermal stability and solvent stability, and has the defect of single coordination mode; the phosphonic acid ligand can form a chemical bond with metal ions, the framework strength is high, the water stability is good, the preparation conditions of the compound are mild, but the coordination geometrical configuration of the phosphonic acid ligand is more complex and changeable compared with carboxylic acid and nitrogen heterocyclic ligand, a compact structure is easy to generate, and a product with a uniform crystal phase is difficult to obtain. Therefore, a coordination polymer is constructed by utilizing a strategy of mixed functional group ligands, and other coordination functional groups (such as pyrazole, triazole, carboxylic acid and the like) are bonded to the organic phosphonic acid ligand in a covalent bond mode, so that a novel ligand containing the mixed functional groups is obtained. The ligand can be adjusted from the coordination capability of different ligands, the length of the ligand, the framework structure of the ligand and the like, and the advantages of all the ligands are combined, so that the three-dimensional framework material with higher porosity and larger specific surface is obtained. Then a large number of orderly arranged proton transfer passages are constructed through the hydrogen bond action between the introduced acid-base ion pairs so as to obtain the metal-organic framework type proton conductor material with higher proton conductivity under the conditions of high temperature and low humidity.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a metal-organic framework type proton conductor material suitable for use under high temperature and low humidity conditions and a preparation method thereof, wherein the metal-organic framework type proton conductor material is a microporous self-assembly material constructed based on phosphonic acid-nitrogen heterocyclic aromatic ligands, and the preparation process is relatively simple.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the preparation method of the metal-organic framework type proton conductor material applicable to the high-temperature and low-humidity conditions comprises the following specific steps:
1) according to molar ratio, metal salt: phosphonic acid-azacyclic aromatic ligands: 0.1-10% of organic amine: 1: weighing 0.2-5 of the raw materials for later use;
2) adding the raw material metal salt, the phosphonic acid-nitrogen heterocyclic aromatic ligand and the organic amine weighed in the step 1) into a solvent, stirring at room temperature to obtain uniform sol, transferring the sol into a hydrothermal reaction kettle for hydrothermal reaction, cooling the reaction solution to room temperature after the reaction is finished to separate out crystals, and filtering, washing and drying to obtain the metal-organic framework type proton conductor material applicable to the high-temperature and low-humidity conditions.
According to the scheme, the metal salt in the step 1) is one of nitrate, chloride, sulfate and acetate of transition metal, or nitrate, chloride, sulfate and acetate of rare earth (lanthanide) metal, or a mixture of several of the nitrate, chloride, sulfate and acetate. When the metal salt is rare earth (lanthanide) metal salt, alkali is added into the system to adjust the pH value to be neutral.
Preferably, the metal salt in step 1) is Co (NO)3)2·6H2O、CoCl2·6H2O、CoSO4·7H2O、FeSO4、FeCl2、FeCl3、Fe(NO3)3、CrCl3、Cr(NO3)3、CdCl2、CdSO4、Cd(NO3)2、NiCl2、NiSO4、Ni(NO3)2、CuCl2、CuSO4、Cu(NO3)2、Cu(CH3COO)2、ZnCl2、ZnSO4、Zn(NO3)2、Zn(CH3COO)2·2H2O、Ce(NO3)3·6H2O、CeCl3、Ce2(SO4)3、Tb(NO3)3、TbCl3、Eu(NO3)3·6H2O、EuCl3One or a mixture of several of them.
According to the scheme, the phosphonic acid-nitrogen heterocyclic aromatic ligand in the step 1) is p4- (1H-pyrazole) benzene phosphonic acid, 3, 5-dimethyl-4- (1H-pyrazole) benzene phosphonic acid, p4- (1,3, 4-triazole) benzene phosphonic acid (H)2ptz), p4- [ (1,3, 4-triazol-1-yl) amino]Benzenephosphonic acid (H)2patz), or a mixture of several of them.
According to the scheme, the organic amine in the step 1) is one or a mixture of triethylamine, N ' -Dimethylformamide (DMF), N ' -Dimethylacetamide (DMAC), N ' -Diethylformamide (DEF), dimethylamine and methylamine.
Preferably, the molar ratio of metal salt in step 1): phosphonic acid-azacyclic aromatic ligands: 0.3-3% of organic amine: 1: 0.5 to 4.
According to the scheme, the solvent in the step 2) is distilled water or a mixed solvent of alcohol and distilled water, wherein the alcohol is one or a mixture of methanol, ethanol, propanol, isopropanol, n-butanol and isobutanol, and the volume ratio of the alcohol to the distilled water in the mixed solvent is alcohol: distilled water 1: 4-2: 3.
according to the scheme, the concentration of the phosphonic acid-nitrogen heterocyclic aromatic ligand in the sol in the step 2) is 0.02-0.1 mol/L.
According to the scheme, the stirring time of the step 2) at room temperature is 0.5-2 h.
According to the scheme, the hydrothermal reaction conditions in the step 2) are as follows: reacting for 8-72 h at 60-200 ℃.
Preferably, the cooling rate in step 2) is 5 ℃/h.
The invention also provides a preparation method of the metal-organic framework type proton conductor material applicable under the high-temperature and low-humidity conditions, which comprises the following specific steps:
1) according to molar ratio, metal salt: phosphonic acid-azacyclic aromatic ligands: 0.1-10% of organic amine: 1: weighing 0.2-5 of the raw materials for later use;
2) adding the raw material metal salt, the phosphonic acid-nitrogen heterocyclic aromatic ligand and the organic amine weighed in the step 1) into a solvent, stirring at room temperature to obtain uniform sol, transferring the sol into a hydrothermal reaction kettle for hydrothermal reaction, cooling the reaction solution to room temperature after the reaction is finished to separate out crystals, and filtering, washing and drying to obtain the metal-organic framework type proton conductor material applicable to the high-temperature and low-humidity conditions.
In the invention, the adopted ligand is a phosphonic acid-nitrogen heterocyclic organic ligand formed by modifying nitrogen heterocyclic ring and phosphonic acid on a benzene ring, the ligand effectively utilizes the good water stability of the nitrogen heterocyclic ring and the multi-coordination site characteristic of phosphonic acid groups, and simultaneously, the orderly arranged phosphonic acid groups also provide possibility for realizing proton conduction. In addition, adjacent metal ions are connected through N-N bridges and O-P-O bridges on the phosphonic acid-nitrogen heterocyclic organic ligand to form an extended one-dimensional chain. The adjacent one-dimensional chains are linked together through ligands to form a two-dimensional layered structure. In the vertical direction, the layers are connected through hydrogen bonds among the uncoordinated phosphonic acid groups, and further stacked into a three-dimensional framework structure with one-dimensional pore channels. When the acid-base pair is applied to a pore channel constructed on the basis of the phosphonic acid-nitrogen heterocyclic ligand, a large number of orderly arranged proton transfer channels are constructed by uncoordinated oxygen atoms on the phosphonic acid group and ions which can serve as proton carriers through hydrogen bond action, the activation energy for transferring protons in the proton transfer channels is smaller by combining the strong chemical bond advantage between the acid-base pair, and the thermal stability and the structural stability of the metal-organic framework type proton conductor material are obviously enhanced due to the existence of a benzene ring structure in the ligand. Therefore, the material has the characteristics of high porosity and large specific surface area of MOFs, has excellent conductivity and stability, and has great application value.
The invention has the beneficial effects that: 1. the invention adopts the benzene phosphonic acid ligand modified by the nitrogen heterocycle, not only overcomes the defect that the phosphonic acid coordination polymer is easy to form a compact phase due to multiple binding points, but also has larger volume of the nitrogen heterocycle, and the existence of the benzene ring structure causes the difficulty that water molecules attack the center of metal ions to be increased, so that the prepared proton conductor material has excellent use stability: the organic proton conductor material is placed in an alkaline aqueous solution (pH 13) or an acidic aqueous solution (pH 1) at room temperature, and the material can be stabilized for more than 5 days; or placing the material in boiling water, and maintaining the stabilization period of the material for more than one week. Soaking the material in distilled water for 24 hours to obtain a hydrolysis rate of 2.23-3.16%, wherein the thermal stability temperature is 260-345 ℃; the addition of the organic amine not only plays a role in removing protons, but also can form acid-base ion pairs between cations generated by decomposition at high temperature and oxygen atoms which are not coordinated on a phosphate group, and a large number of orderly arranged proton transfer passages are constructed through the action of hydrogen bonds, so that the anhydrous proton conductivity of the material under the conditions of high temperature and low humidity is improved, the anhydrous conductivity of the organic proton conductor material under the conditions of 140 ℃ and RH 10% is 0.052-0.071S/cm, and the ion exchange capacity is 0.54-0.74 mg/mol; 2. the preparation method provided by the invention is simple in process and mild in conditions, and can be used for large-scale and batch production after being properly improved, so that the preparation method has a good production basis and a wide application prospect.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail with reference to the following examples.
Example 1
A metal-organic framework type proton conductor material based on phosphonic acid-azole aromatic ligand is prepared by the following specific steps:
(1) 0.146g of Co (NO)3)2·6H2O(0.5mmol)、0.120g H2Patz (0.5mmol) and 0.058g DMF (0.8mmol) were addedStirring the mixture for 1 hour at room temperature in a mixed solvent consisting of 2mL of ethanol and 8mL of distilled water to obtain dark red uniform sol;
(2) transferring the sol into a 25mL stainless steel hot kettle lined with polytetrafluoroethylene, sealing, and then placing in a constant-temperature oven at 120 ℃ for reaction for 48 hours;
(3) the reaction solution is cooled to room temperature at the speed of 5 ℃/h, and reddish brown flaky crystals are obtained after filtration. And repeatedly washing the crystal with deionized water for three times, and drying in a vacuum oven at 50 ℃ for 1h to obtain the metal-organic framework type proton conductor material. The results of the basic physical property tests are shown in Table 1.
Example 2
A metal-organic framework type proton conductor material based on phosphonic acid-azole aromatic ligand is prepared by the following specific steps:
(1) 0.119g of CoCl2·6H2O(0.5mmol)、0.120g H2Adding patz (0.5mmol) and 0.109g DMAC (1.25mmol) into a mixed solvent consisting of 2mL methanol and 8mL distilled water, and stirring for 1h at room temperature to obtain a deep red uniform sol;
(2) transferring the sol into a 25mL stainless steel hot kettle lined with polytetrafluoroethylene, sealing, and then placing in a constant-temperature oven at 140 ℃ for reaction for 48 hours;
(3) cooling the reaction solution to room temperature at the speed of 5 ℃/h, filtering to obtain red rod-shaped crystals, repeatedly washing the crystals for three times by using deionized water, and drying in a vacuum oven at the temperature of 50 ℃ for 1h to obtain the metal-organic framework type proton conductor material, wherein the test results of the basic physical properties are shown in Table 1.
Example 3
A metal-organic framework type proton conductor material based on phosphonic acid-azole aromatic ligand is prepared by the following specific steps:
(1) 0.141g of CoSO4·7H2O(0.5mmol)、0.120g H2Adding patz (0.5mmol) and 0.087g DMAC (1mmol) into a mixed solvent consisting of 4mL of ethanol and 6mL of distilled water, and stirring for 1h at room temperature to obtain rose uniform sol;
(2) transferring the sol into a 25mL stainless steel hot kettle lined with polytetrafluoroethylene, sealing, and then placing in a constant-temperature oven at 120 ℃ for reaction for 48 hours;
(3) cooling the reaction solution to room temperature at the speed of 5 ℃/h, filtering to obtain red rod-shaped crystals, repeatedly washing the crystals for three times by using deionized water, and drying in a vacuum oven at the temperature of 50 ℃ for 1h to obtain the metal-organic framework type proton conductor material, wherein the test results of the basic physical properties are shown in Table 1.
Example 4
A metal-organic framework type proton conductor material based on phosphonic acid-azole aromatic ligand is prepared by the following specific steps:
(1) 0.217g Ce (NO)3)3·6H2O(0.5mmol)、0.120g H2Adding patz (0.5mmol) and 0.110g DMF (1.5mmol) into 10mL of distilled water, adding 0.044g NaOH to adjust the pH value of the system to be neutral, and stirring for 1h at room temperature to obtain reddish uniform sol;
(2) transferring the sol into a 25mL stainless steel hot kettle lined with polytetrafluoroethylene, sealing, and then placing in a constant-temperature oven at 160 ℃ for reaction for 72 hours;
(3) cooling the reaction solution to room temperature at the speed of 5 ℃/h, filtering to obtain colorless transparent crystals, repeatedly washing the crystals for three times by using deionized water, and drying in a vacuum oven at the temperature of 60 ℃ for 1h to obtain the metal-organic framework type proton conductor material, wherein the test results of the basic physical properties are shown in table 1.
Example 5
A metal-organic framework type proton conductor material based on phosphonic acid-pyrazole aromatic ligand is prepared by the following specific steps:
(1) 0.087g of Co (NO)3)2·6H2O (0.3mmol), 0.078g p4- (1H-pyrazole) phenylphosphonic acid (0.35mmol) and 0.039g DMAC (0.45mmol) are added into a mixed solvent consisting of 2mL of ethanol and 8mL of distilled water, and stirred for 1H at room temperature to obtain a reddish brown uniform sol;
(2) transferring the sol into a 25mL stainless steel hot kettle lined with polytetrafluoroethylene, sealing, and then placing in a constant-temperature oven at 120 ℃ for reaction for 24 hours;
(3) cooling the reaction solution to room temperature at the speed of 5 ℃/h, filtering to obtain red flaky crystals, repeatedly washing the crystals for three times by using deionized water, and drying in a vacuum oven at the temperature of 60 ℃ for 1h to obtain the metal-organic framework type proton conductor material, wherein the test results of the basic physical properties are shown in Table 1.
Example 6
A metal-organic framework type proton conductor material based on phosphonic acid-azole aromatic ligand is prepared by the following specific steps:
(1) 0.146g of Co (NO)3)2·6H2O (0.5mmol), 0.113g p4- (1,3, 4-triazole) phenylphosphonic acid (H)2ptz) (0.5mmol) and 0.058g DMF (0.8mmol) were added to a mixed solvent consisting of 2mL ethanol and 8mL distilled water, and after stirring for 1h at room temperature, a dark red homogeneous sol was obtained;
(2) transferring the sol into a 25mL stainless steel hot kettle lined with polytetrafluoroethylene, sealing, and then placing in a constant-temperature oven at 120 ℃ for reaction for 48 hours;
(3) cooling the reaction solution to room temperature at the speed of 5 ℃/h, filtering to obtain a reddish brown flaky crystal, repeatedly washing the crystal three times by using deionized water, and drying in a vacuum oven at the temperature of 50 ℃ for 1h to obtain the metal-organic framework type proton conductor material, wherein the test results of the basic physical properties are shown in table 1.
Example 7
A metal-organic framework type proton conductor material based on phosphonic acid-azole aromatic ligand is prepared by the following specific steps:
(1) 0.223g Eu (NO)3)3·6H2O (0.5mmol), 0.124g p4- (1,3, 4-triazole) phenylphosphonic acid (H)2ptz) (0.55mmol) and 0.110g DMF (1.5mmol) are added into 10mL distilled water, then 0.048g NaOH is added to adjust the pH value to be neutral, and after stirring for 1h at room temperature, light pink uniform sol is obtained;
(2) transferring the sol into a 25mL stainless steel hot kettle lined with polytetrafluoroethylene, sealing, and then placing in a constant-temperature oven at 160 ℃ for reaction for 72 hours;
(3) cooling the reaction solution to room temperature at the speed of 5 ℃/h, filtering to obtain colorless hexahedral crystals, repeatedly washing the crystals for three times by using deionized water, and drying in a vacuum oven at the temperature of 60 ℃ for 1h to obtain the metal-organic framework type proton conductor material, wherein the test results of the basic physical properties are shown in table 1.
Example 8
Based on H2patz and p4- (1,3, 4-triazole) phenylphosphonic acid (H)2ptz) the specific preparation steps of the metal-organic framework type proton conductor material of the mixed ligand are as follows:
(1) 0.110g of Zn (CH)3COO)2·2H2O(0.5mmol)、0.120g H2patz(0.5mmol)、0.0225g H2ptz (0.1mmol) and 0.110g DMF (1.5mmol) are added into a mixed solvent consisting of 4mL ethanol and 6mL distilled water, and stirred for 1h at room temperature to obtain milk white uniform sol;
(2) transferring the sol into a 25mL stainless steel hot kettle lined with polytetrafluoroethylene, sealing, and then placing in a constant-temperature oven at 140 ℃ for reaction for 72 hours;
(3) cooling the reaction solution to room temperature at the speed of 5 ℃/h, filtering to obtain colorless flaky crystals, repeatedly washing the crystals for three times by using deionized water, and drying in a vacuum oven at the temperature of 60 ℃ for 1h to obtain the metal-organic framework type proton conductor material, wherein the test results of the basic physical properties are shown in Table 1.
Example 9
Based on H2The preparation method of the metal-organic framework type proton conductor material of the mixed ligand consisting of the patz and the p4- (1H-pyrazole) benzene phosphonic acid comprises the following specific steps:
(1) 0.110g of Zn (CH)3COO)2·2H2O(0.5mmol)、0.120g H2Adding patz (0.5mmol), 0.022gp4- (1H-pyrazole) phenylphosphonic acid (0.1mmol) and 0.110g DMF (1.5mmol) into a mixed solvent consisting of 4mL of ethanol and 6mL of distilled water, and stirring at room temperature for 1H to obtain a milky uniform sol;
(2) transferring the sol into a 25mL stainless steel hot kettle lined with polytetrafluoroethylene, sealing, and then placing in a constant-temperature oven at 140 ℃ for reaction for 72 hours;
(3) cooling the reaction solution to room temperature at the speed of 5 ℃/h, filtering to obtain colorless blocky crystals, repeatedly washing the crystals for three times by using deionized water, and drying in a vacuum oven at the temperature of 60 ℃ for 1h to obtain the metal-organic framework type proton conductor material, wherein the test results of the basic physical properties are shown in table 1.
TABLE 1 results of performance test of the metal-organic framework type proton conductor materials prepared in examples 1 to 9
The anhydrous conductivities in Table 1 were measured at 140 ℃ and RH 10%. The metal-organic framework type proton conductor material based on the phosphonic acid-nitrogen heterocyclic aromatic ligand can provide higher conductivity (0.052-0.071S/cm), and can basically meet the high-temperature membrane conductivity requirement (the conductivity needs to reach 0.05-0.1S/cm under the conditions of 120 ℃ and RH 50%) provided by the United states department of energy. In addition, the metal-organic framework type proton conductor material synthesized by the method has excellent stability, the hydrolysis rate of the material is kept between 2.23 and 3.16 percent after the material is soaked in distilled water for 24 hours, and the thermal stability temperature range is 260 to 345 ℃.
It is to be understood that the above examples are merely for purposes of clearly illustrating the present invention and are not to be construed as limiting the embodiments. The values of the upper limit and the lower limit and the interval of the raw materials listed in the invention, and the values of the upper limit and the lower limit and the interval of the process parameters (such as temperature, time, pressure, pH and the like) can realize the invention, and all the implementation cases do not need to be listed one by one, but obvious changes or variations are still within the protection scope created by the invention.
Claims (5)
1. A metal-organic framework type proton conductor material applicable under the conditions of high temperature and low humidity is characterized in that the preparation method comprises the following specific steps:
1) according to molar ratio, metal salt: phosphonic acid-azacyclic aromatic ligands: organic amine = 0.1-10: 1: weighing 0.2-5 of the raw materials for later use;
2) adding the raw material metal salt, phosphonic acid-nitrogen heterocyclic aromatic ligand and organic amine weighed in the step 1) into a solvent, stirring at room temperature to obtain uniform sol, transferring the sol into a hydrothermal reaction kettle for hydrothermal reaction, cooling the reaction solution to room temperature after the reaction is finished to separate out crystals, and filtering, washing and drying to obtain a metal-organic framework type proton conductor material applicable under the conditions of high temperature and low humidity;
step 1), the metal salt is one of nitrate, chloride, sulfate and acetate of transition metal, or nitrate, chloride, sulfate and acetate of rare earth lanthanide metal, or a mixture of a plurality of the nitrate, chloride, sulfate and acetate of the rare earth lanthanide metal, and when the metal salt is the rare earth lanthanide metal salt, alkali is added into a system to adjust the pH value to be neutral;
the phosphonic acid-nitrogen heterocyclic aromatic ligand in the step 1) is one of p4- (1H-pyrazole) phenylphosphonic acid, 3, 5-dimethyl-4- (1H-pyrazole) phenylphosphonic acid, p4- (1,3, 4-triazole) phenylphosphonic acid and p4- [ (1,3, 4-triazole-1-yl) amino ] phenylphosphonic acid, or a mixture of several of the above;
the organic amine in the step 1) is triethylamine,N,N’-dimethylformamide,N,N’-dimethylacetamide,N, N’-one or a mixture of several of diethylformamide, dimethylamine and methylamine;
step 2) the hydrothermal reaction conditions are as follows: reacting for 8-72 h at 60-200 ℃;
and 2) the cooling rate is 5 ℃/h.
2. The metal-organic framework type proton conductor material according to claim 1, wherein the metal salt in step 1) is Co (NO)3）2·6H2O、CoCl2·6H2O、CoSO4·7H2O、FeSO4、FeCl2、FeCl3、Fe（NO3）3、CrCl3、Cr（NO3）3、CdCl2、CdSO4、Cd（NO3）2、NiCl2、NiSO4、Ni（NO3）2、CuCl2、CuSO4、Cu（NO3）2、Cu（CH3COO）2、ZnCl2、ZnSO4、Zn（NO3）2、Zn（CH3COO）2·2H2O、Ce（NO3）3·6H2O、CeCl3、Ce2（SO4）3、Tb（NO3）3、TbCl3、Eu（NO3）3·6H2O、EuCl3One or a mixture of several of them.
3. The metal-organic framework type proton conductor material suitable for use under high temperature and low humidity conditions as claimed in claim 1, wherein the solvent in step 2) is distilled water, or a mixed solvent of alcohols and distilled water, wherein the alcohols are one or more of methanol, ethanol, propanol, isopropanol, n-butanol and isobutanol, and the volume ratio of the alcohols to the distilled water in the mixed solvent is alcohol: distilled water = 1: 4-2: 3.
4. the metal-organic framework proton conductor material applicable under high temperature and low humidity conditions as claimed in claim 1, wherein the concentration of the phosphonic acid-nitrogen heterocyclic aromatic ligand in the sol of step 2) is 0.02-0.1 mol/L.
5. A method for preparing a metal-organic framework type proton conductor material suitable for use under high temperature and low humidity conditions according to any one of claims 1 to 4, comprising the following steps:
1) according to molar ratio, metal salt: phosphonic acid-azacyclic aromatic ligands: organic amine = 0.1-10: 1: weighing 0.2-5 of the raw materials for later use;
2) adding the raw material metal salt, the phosphonic acid-nitrogen heterocyclic aromatic ligand and the organic amine weighed in the step 1) into a solvent, stirring at room temperature to obtain uniform sol, transferring the sol into a hydrothermal reaction kettle for hydrothermal reaction, cooling the reaction solution to room temperature after the reaction is finished to separate out crystals, and filtering, washing and drying to obtain the metal-organic framework type proton conductor material applicable to the high-temperature and low-humidity conditions.
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