CN116444811A - Metal organic framework material and preparation method and application thereof - Google Patents
Metal organic framework material and preparation method and application thereof Download PDFInfo
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- CN116444811A CN116444811A CN202310412220.4A CN202310412220A CN116444811A CN 116444811 A CN116444811 A CN 116444811A CN 202310412220 A CN202310412220 A CN 202310412220A CN 116444811 A CN116444811 A CN 116444811A
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 73
- -1 rare earth metal ions Chemical class 0.000 claims abstract description 36
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 30
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000004020 conductor Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 239000003446 ligand Substances 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical class OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000013141 crystalline metal-organic framework Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Polymers & Plastics (AREA)
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Abstract
The invention provides a metal organic framework material and a preparation method thereof, belonging to the technical field of proton conductor materials. The metal organic framework material provided by the invention is a crystalline porous material formed by coordination of rare earth metal ions and oxalic acid, and the diameter of an inner pore canal of the metal organic framework material is smaller than 1nm. The metal organic framework material provided by the invention takes oxalic acid as a ligand and rare earth metal ions as coordination metals, a compact hydrogen bond network can be formed inside the metal organic framework material, the diameter of an internal pore canal is smaller than 1nm, and the metal organic framework material is favorable for maintaining a complete proton transmission path under the condition of low relative humidity, so that good low-humidity proton conduction performance is obtained.
Description
Technical Field
The invention relates to the technical field of proton conductor materials, in particular to a metal organic framework material and a preparation method and application thereof.
Background
Currently, the commercially used conductive materials are based on perfluorosulfonic acids, which have a value of higher than 10 at 60-80 ℃ and 98% RH (relative humidity) -2 S·cm -1 However, perfluorosulfonic acid has problems of high price and complicated manufacturing process, which limits its application. The crystalline metal organic framework material can be provided withThe characteristics of meter and directional synthesis are widely studied and applied in the fields of catalysis, solid electrolyte, selective adsorption, fluorescence identification and the like.
Among the metal organic framework material compounds that have been reported so far, la (H 5 DTMP)·7H 2 O(σ＝8×10 - 3 S·cm -1 24 ℃,98% rh), and [ Me ] 2 NH 2 ][Eu(ox) 2 (H 2 O)]·3H 2 O(σ＝2.73×10 -3 S·cm -1 55 ℃,95% rh) has good proton conductivity results, but these compounds need to maintain good proton conductivity in high relative humidity environments with a relative humidity of 95-100%. However, the existing metal organic framework compounds diffuse hydrogen ions through the water beam formed in the hydrophilic channel (ion conducting channel), and thus, when the ambient relative humidity is low, such as below 60% rh, the ion conductivity is greatly reduced, and the conductivity is low.
Disclosure of Invention
The invention aims to provide a metal organic framework material which can still have higher conductivity in a low humidity environment, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a metal organic framework material which is a crystalline porous material formed by coordination of rare earth metal ions and oxalic acid, wherein the diameter of an inner pore canal of the metal organic framework material is smaller than 1nm.
Preferably, the metal organic framework material has a molecular formula (N 2 H 5 )Ln 2 (C 2 O 4 ) 4 (N 2 H 5 )]·4H 2 O。
Preferably, the rare earth metal ions comprise metal clusters formed by one or more of neodymium, cerium, and praseodymium.
The invention also provides a preparation method of the metal organic framework material, which comprises the following steps: mixing water-soluble rare earth metal salt, oxalic acid, hydrazine hydrate and deionized water, and performing hydrothermal reaction to obtain the metal organic framework material.
Preferably, the water-soluble rare earth metal salt comprises one or more of neodymium nitrate, cerium nitrate, and praseodymium nitrate.
Preferably, the mass ratio of oxalic acid, hydrazine hydrate and water-soluble rare earth metal salt is 2.5:5:0.8-2.5:5:1.2.
Preferably, the temperature of the hydrothermal reaction is 140-160 ℃.
Preferably, the hydrothermal reaction time is 72-120 hours.
The invention also provides the metal organic frame material or the application of the metal organic frame material obtained by the preparation method in the technical scheme as a proton conductor, wherein the environmental humidity of the proton conductor application is lower than 60%.
The invention provides a metal organic framework material which is a crystalline porous material formed by coordination of rare earth metal ions and oxalic acid, wherein the diameter of an inner pore canal of the metal organic framework material is smaller than 1nm. According to the metal organic framework material provided by the invention, oxalic acid is used as an organic ligand, rare earth metal ions are used as coordination metals, a compact hydrogen bond network can be formed inside the metal organic framework material, so that the diameter of an internal pore canal is smaller than 1nm, and the metal organic framework material is favorable for maintaining a complete proton transmission path under the condition of low relative humidity, thereby obtaining better low-humidity proton conduction performance. Experimental results show that the proton conductivity of the metal organic framework material provided by the invention can reach 1.23 multiplied by 10 at 60% relative humidity -5 S·cm -1 。
Drawings
FIG. 1 is a crystal structure diagram of a metal organic framework material prepared in example 1 of the present invention;
FIG. 2 is a diagram showing the structure of a skeletal hydrogen bond network of the metal organic framework material prepared in example 1 of the present invention;
fig. 3 is a graph showing the results of conductivity testing at 60% relative humidity for the metal-organic framework material of example 1 of the present invention.
Detailed Description
The invention provides a metal organic framework material which is a crystalline porous material formed by coordination of rare earth metal ions and oxalic acid, wherein the diameter of an inner pore canal of the metal organic framework material is smaller than 1nm.
In the present invention, the metal organic framework material has a molecular formula of (N 2 H 5 )Ln 2 (C 2 O 4 ) 4 (N 2 H 5 )]·4H 2 O。
In the present invention, the rare earth metal ion preferably includes a metal cluster formed of one or more of neodymium, cerium, and praseodymium, more preferably neodymium. In the present invention, the rare earth metal is used as a coordinating metal, and can form a metal organic framework material with a dense hydrogen bond network inside with a ligand.
In the invention, oxalic acid is used as a ligand, rare earth metal ions are used as coordination metal ions, and the crystalline porous material is formed through coordination, and is internally provided with a compact hydrogen bond network, and the diameter of a pore canal is smaller than 1nm, so that the complete proton transmission path is maintained under the condition of low relative humidity, and the good low-humidity proton conduction performance is obtained.
The invention also provides a preparation method of the metal organic framework material, which comprises the following steps: mixing water-soluble rare earth metal salt, oxalic acid, hydrazine hydrate and deionized water, and performing hydrothermal reaction to obtain the metal organic framework material.
In the present invention, the water-soluble rare earth metal salt preferably includes one or more of neodymium nitrate, cerium nitrate, and praseodymium nitrate, more preferably neodymium nitrate. In the present invention, the water-soluble rare earth metal salt has water solubility, and provides the metal organic framework material with the required metal ions.
In the invention, because the oxalic acid skeleton is negatively charged, the hydrazine hydrate is used as a counter ion to form a hydrogen bond with oxalic acid, so that a compact hydrogen bond network is formed inside a crystalline porous material formed by coordination of metal ions and oxalic acid.
In the invention, the oxalic acid is used as an organic ligand and can be connected with rare earth metal through coordination to form a porous crystal material.
In the present invention, the deionized water provides the solvent required for dissolution of the raw materials. The dosage of the deionized water is not particularly limited, and the deionized water can be adjusted according to the reaction container.
In the present invention, the ratio of the amounts of the oxalic acid, hydrazine hydrate and the water-soluble rare earth metal salt is preferably 2.5:5:0.8 to 2.5:5:1.2, more preferably 2.5:5:0.9 to 2.5:5:1.0. In the invention, when the mass ratio of oxalic acid, hydrazine hydrate and water-soluble rare earth metal salt is in the above range, the components are promoted to react fully, and the purer metal-organic frame material is obtained.
The method for mixing the water-soluble rare earth metal salt, oxalic acid, hydrazine hydrate and deionized water is not particularly limited, and the water-soluble rare earth metal salt, oxalic acid and hydrazine hydrate can be dissolved in deionized water by adopting a mixing method well known to those skilled in the art. In the present invention, the mixing is preferably performed under stirring.
In the present invention, the temperature of the hydrothermal reaction is preferably 140 to 160 ℃, more preferably 150 to 160 ℃; the time of the hydrothermal reaction is preferably 72 to 120 hours, more preferably 72 hours. In the invention, rare earth metal ions are reduced into metal clusters in the hydrothermal reaction process, and the metal clusters and oxalic acid undergo coordination reaction to form the crystalline porous material. In the invention, the temperature and time of the hydrothermal reaction are adopted, so that the reaction can be promoted to be fully carried out, and the purer metal-organic framework material can be obtained.
The apparatus for the hydrothermal reaction is not particularly limited, and any hydrothermal reaction apparatus known to those skilled in the art may be used. In the invention, the device for the hydrothermal reaction is preferably a polytetrafluoroethylene reaction kettle.
After the hydrothermal reaction is completed, the invention preferably collects the sediment of the product of the hydrothermal reaction, and washes and dries the collected sediment to obtain the metal organic framework material.
The method of collecting the precipitate is not particularly limited in the present invention, and the method of collecting the precipitate known to those skilled in the art may be employed. In the present invention, the means for collecting the precipitate is preferably centrifugation. In the present invention, the washing reagent is preferably deionized water. The mode and the number of times of washing are not particularly limited in the present invention, and impurities in the precipitate can be removed by using the mode and the number of times of washing, which are well known to those skilled in the art.
In the present invention, the drying temperature is preferably 50 to 80 ℃, more preferably 60 to 70 ℃; the drying time is preferably 18 to 36 hours, more preferably 24 to 32 hours. In the present invention, when the temperature and time of the drying are within the above ranges, the precipitate can be sufficiently dried without damaging the structure of the precipitate. The drying apparatus is not particularly limited, and a drying apparatus known to those skilled in the art may be used. In the present invention, the drying apparatus is preferably an oven.
The invention also provides the metal organic frame material and application of the metal organic frame material prepared by the preparation method in the technical scheme as a proton conductor.
The mode of application of the present invention is not particularly limited, and proton conductor application modes known to those skilled in the art may be employed.
In the present invention, the environmental humidity for the proton conductor application is preferably less than 60%, more preferably less than 55%. The metal organic framework material provided by the invention is internally provided with a compact hydrogen bond network, the diameter of an internal pore canal is smaller than 1nm, the complete proton transmission path can be maintained under the condition of low relative humidity of less than 60%, and the metal organic framework material has good low-humidity proton conduction performance.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Raw materials: the organic ligand is oxalic acid and the molecular formula is H 2 C 2 O 4 ·2H 2 O; the water-soluble rare earth metal salt is neodymium nitrate, and the molecular formula is Nd (NO) 3 ) 3 ·6H 2 O; hydrazine hydrate with molecular formula of N 2 H 4 ·2H 2 O, the reaction solvent is deionized water.
In this embodiment, H 2 C 2 O 4 、N 2 H 4 ·2H 2 O and Nd (NO) 3 ) 3 ·6H 2 The ratio of the amounts of O species was 2.5:5:1.
Weighing 2.5mmolH 2 C 2 O 4 ·2H 2 O and 5mmolN 2 H 4 ·2H 2 O is dissolved in 10mL of deionized water under stirring to obtain a mixed solution, and 10mL of the mixed solution is added into a polytetrafluoroethylene reaction kettle liner; weighing 1mmolNd (NO) 3 ) 3 ·6H 2 O is added into a polytetrafluoroethylene reaction kettle to be sealed and then is put into an oven to carry out hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 150 ℃, and the reaction time is 72 hours. And (3) obtaining white solid after the reaction is finished, and washing the white solid with deionized water for a plurality of times to obtain the metal organic framework material. According to reactant Nd (NO) 3 ) 3 ·6H 2 The yield of the product was 105% and the purity of the product was 99% calculated on O.
The metal organic framework material prepared in this example was tested using a single crystal x-ray diffractometer, and the crystal structure obtained by single crystal XRD analysis is shown in fig. 1. In fig. 1, (a) and (b) are coordination environments of rare earth ions; (c) - (e) are ligand configurations of oxalic acid; (f) is a top view of the three-dimensional skeletal structure along the a-axis; and (g) is a detail view in the dashed line box of the figure (f).
Fig. 2 is a diagram showing a structure of hydrogen bond network of the metal organic framework material skeleton prepared in this example. As can be seen from fig. 2, the metal organic framework material prepared in this embodiment can form a dense hydrogen bond network inside the pore canal.
Example 2
In this embodiment, H 2 C 2 O 4 、N 2 H 4 ·2H 2 O and Nd (NO) 3 ) 3 ·6H 2 The ratio of the amounts of O species was 2.5:5:0.8.
Weighing 2.5mmolH 2 C 2 O 4 ·2H 2 O and 5mmolN 2 H 4 ·2H 2 O is dissolved in 10mL of deionized water under stirring to obtain a mixed solution, and 10mL of the mixed solution is added into a polytetrafluoroethylene reaction kettle liner; weighing 0.8mmolNd (NO) 3 ) 3 ·6H 2 O is added into a polytetrafluoroethylene reaction kettle to be sealed and then is put into an oven to carry out hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 150 ℃, and the reaction time is 72 hours. And (3) obtaining white solid after the reaction is finished, and washing the white solid with deionized water for a plurality of times to obtain the metal organic framework material. According to reactant Nd (NO) 3 ) 3 ·6H 2 The yield of the product was 98% and the purity of the product was 95% calculated on O.
Example 3
In this embodiment, H 2 C 2 O 4 、N 2 H 4 ·2H 2 O and Nd (NO) 3 ) 3 ·6H 2 The ratio of the amounts of O species was 2.5:5:1.2.
Weighing 2.5mmolH 2 C 2 O 4 ·2H 2 O and 5mmolN 2 H 4 ·2H 2 O is dissolved in 10mL of deionized water under stirring to obtain a mixed solution, and 10mL of the mixed solution is added into a polytetrafluoroethylene reaction kettle liner; weighing 1.2mmolNd (NO) 3 ) 3 ·6H 2 O is added into a polytetrafluoroethylene reaction kettle to be sealed and then is put into an oven to carry out hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 150 ℃, and the reaction time is 72 hours. And (3) obtaining white solid after the reaction is finished, and washing the white solid with deionized water for a plurality of times to obtain the metal organic frame body material. According to reactant Nd (NO) 3 ) 3 ·6H 2 The yield of the product was 102% and the purity of the product was 97% calculated on O.
Test case
The metal organic framework material prepared in example 1 was tested and the proton conductivity diagram at 60% relative humidity is shown in fig. 3. As can be seen from fig. 3, the metal organic framework material provided by the inventionProton conductivity can reach 1.23×10 at 60% relative humidity -5 S·cm -1 Has excellent electrical conductivity.
As can be seen from the above examples, the metal organic framework material provided by the present invention has a proton conductivity of up to 1.23×10 at 60% relative humidity -5 S·cm -1 Has excellent electrical conductivity. The metal organic framework material provided by the invention forms a metal organic framework structure with pore channels with the diameter smaller than 1nm by hybridizing rare earth metal ions and short-chain oxalic acid organic ligands, and the inside of the pore channels of the compound can form a compact hydrogen bond network, so that the complete proton transmission path can be maintained under the condition of low relative humidity, and the good low-humidity proton conduction performance can be obtained.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The metal organic frame material is a crystalline porous material formed by coordination of rare earth metal ions and oxalic acid, and the diameter of an internal pore canal of the metal organic frame material is smaller than 1nm.
2. The metal-organic framework material of claim 1, wherein the metal-organic framework material has a molecular formula (N 2 H 5 )Ln 2 (C 2 O 4 ) 4 (N 2 H 5 )]·4H 2 O。
3. The metal-organic framework material of claim 1 or 2, wherein the rare earth metal ions comprise metal clusters formed from one or more of neodymium, cerium, and praseodymium.
4. A method of preparing a metal organic framework material as claimed in any one of claims 1 to 3 comprising the steps of: mixing water-soluble rare earth metal salt, oxalic acid, hydrazine hydrate and deionized water, and performing hydrothermal reaction to obtain the metal organic framework material.
5. The method of claim 4, wherein the water-soluble rare earth metal salt comprises one or more of neodymium nitrate, cerium nitrate, and praseodymium nitrate.
6. The method according to claim 4, wherein the ratio of the amounts of oxalic acid, hydrazine hydrate and water-soluble rare earth metal salt is 2.5:5:0.8 to 2.5:5:1.2.
7. The method according to claim 4, wherein the hydrothermal reaction is carried out at a temperature of 140 to 160 ℃.
8. The method according to claim 7, wherein the hydrothermal reaction time is 72 to 120 hours.
9. Use of a metal organic framework material according to any one of claims 1 to 3 or a metal organic framework material obtained by a preparation method according to any one of claims 4 to 8 as a proton conductor, said proton conductor being used with an ambient humidity of less than 60%.
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| CN117510888A (en) * | 2024-01-04 | 2024-02-06 | 中国科学院合肥物质科学研究院 | Adsorption-assisted coagulation defluorination polymeric material and preparation method and application thereof |
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| CN106279221A (en) * | 2016-07-13 | 2017-01-04 | 南京工业大学 | A kind of synthetic method of high proton conducting metal organic framework material |
| CN107501565A (en) * | 2017-08-07 | 2017-12-22 | 青海大学 | Rare earth metal organic framework materials Ho MOF and its preparation method and application |
| US20200010486A1 (en) * | 2018-07-05 | 2020-01-09 | Toyota Jidosha Kabushiki Kaisha | Method for producing coordinatively unsaturated metal-organic framework and coordinatively unsaturated metal-organic framework |
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| CN107501565A (en) * | 2017-08-07 | 2017-12-22 | 青海大学 | Rare earth metal organic framework materials Ho MOF and its preparation method and application |
| US20200010486A1 (en) * | 2018-07-05 | 2020-01-09 | Toyota Jidosha Kabushiki Kaisha | Method for producing coordinatively unsaturated metal-organic framework and coordinatively unsaturated metal-organic framework |
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| CN117510888A (en) * | 2024-01-04 | 2024-02-06 | 中国科学院合肥物质科学研究院 | Adsorption-assisted coagulation defluorination polymeric material and preparation method and application thereof |
| CN117510888B (en) * | 2024-01-04 | 2024-04-02 | 中国科学院合肥物质科学研究院 | Adsorption-assisted coagulation defluorination polymeric material and preparation method and application thereof |
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