Microporous metal organic framework material used as getter of vacuum insulation board and synthetic method thereof
Technical Field
The invention relates to a microporous metal organic framework material used as a getter of a vacuum insulation board and a synthesis method thereof.
Background
The vacuum heat insulation board is a novel high-efficiency heat insulation material, is prepared by filling a porous core material, wrapping the porous core material by using an air barrier film and then vacuumizing the air barrier film, and can effectively avoid heat transfer caused by air convection by utilizing the vacuum heat insulation principle, so that the heat conductivity coefficient can be greatly reduced. In the past, the vacuum insulation panel is mainly applied to the fields of military and national defense and the like, and along with the commercialization and cost reduction of the vacuum insulation panel, the vacuum insulation panel has been widely applied to the fields of refrigerators, freezers, electric water heaters, vending machines, freezers, refrigerated containers, heat transmission pipelines, nuclear power facilities, building wall insulation and the like. Compared with other heat-insulating materials, the vacuum heat-insulating plate has low heat conductivity coefficient, has the advantages of thin thickness, small volume and light weight of the heat-insulating layer when the heat-insulating technical requirements are the same, and is suitable for products with higher energy-saving requirements. In the long-term use process of the vacuum heat insulation plate, external air and moisture can gradually permeate into the heat insulation plate along with the time, and in addition, the filled core material can slowly release some gas, so that the vacuum degree is continuously reduced, the heat insulation performance is reduced, and the service life of a product is ended. In order to solve this problem, it is usually necessary to add a getter to absorb these gases, so that the insulation board can maintain a high degree of vacuum and maintain a low thermal conductivity, and finally, the service life of the vacuum insulation board is prolonged. Therefore, the good and bad adsorption performance of the getter is very important for improving the practical service life of the heat insulation plate. At present, the commonly used getters mainly comprise calcium oxide, iron powder, barium-lithium alloy and the like, however, the getters have limited adsorption capacity to gas and water vapor, and the heat conductivity coefficient is generally higher than that of a filled core material, so that the heat insulation effect of the getter position in the prepared heat insulation board is the worst. Compared with the traditional porous material, the microporous metal organic framework material has the advantages of large specific surface area, large adsorption capacity, low heat conductivity coefficient and the like, and is expected to replace the traditional getter to be applied to a heat insulation board.
Disclosure of Invention
The invention aims to provide a microporous metal organic framework material used as a getter of a vacuum insulation board, which has the following structural general formula: m6(μ3-OH)8Lx, wherein M is Zr, Yb, Er, Gd, Y and Ti, L is 2, 5-dimethyl terephthalic acid, 2, 5-diethyl terephthalic acid, 3, 5-dimethyl terephthalic acid, 3, 5-diethoxy terephthalic acid and [2,2' -bipyridyl]5,5 '-dicarboxylic acid, 2',5 '-dimethyl- [1,1':4',1' -terphenyl]-4,4 "-dicarboxylic acid, 2',5' -dipropyl- [1,1':4', 1" -terphenyl]-4,4 "-dicarboxylic acid, 2',5' -dimethoxy- [1,1':4', 1" -terphenyl]-4,4 "-dicarboxylic acid, x ═ 6, 9 or 12. The invention relates to a method for synthesizing a microporous metal organic framework material, which comprises the following steps:
(1) mixing the metal salt containing M and the organic ligand L according to the ratio of 1: 1-4, mixing and dissolving in water or an organic solvent to prepare a solution;
(2) adding a template agent into the solution and uniformly stirring, wherein the ratio of the organic ligand L to the template agent is 1: 1;
(3) and adding acid accounting for 1-6% of the total volume of the solution into the solution, uniformly stirring, putting into a closed hydrothermal kettle, reacting at a constant temperature of 70-150 ℃ for 2-8 days, naturally cooling to room temperature, performing centrifugal separation, and cleaning to obtain the microporous metal organic framework material.
The metal salt containing M in the synthesis method is zirconium nitrate, zirconium chloride, zirconium acetate, ytterbium nitrate, ytterbium acetate, ytterbium chloride, erbium nitrate, erbium chloride, erbium acetate, gadolinium nitrate, yttrium acetate, titanium nitrate and titanium chloride; the organic ligand L is 2, 5-dimethyl terephthalic acid, 2, 5-diethyl terephthalic acid, 3, 5-dimethyl terephthalic acid, 3, 5-diethoxy terephthalic acid, [2,2 '-bipyridyl ] -5,5' -dicarboxylic acid, 2',5' -dimethyl- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid, 2',5' -dipropyl- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid, 2',5' -dimethoxy- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid; the organic solvent is any one or a mixture of several of N, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide, dimethyl sulfoxide, ethanol, dioxane and tetrahydrofuran according to any ratio; the template agent is o-fluorobenzoic acid, o-chlorobenzoic acid, o-bromobenzoic acid, o-methylbenzoic acid and o-ethylbenzoic acid; the acid is hydrochloric acid, nitric acid, acetic acid and tetrafluoroboric acid.
The invention has the beneficial effects that:
1. the microporous metal organic framework material has the advantages of high crystallization degree, nano-scale crystal size, simple synthesis process, high yield and the like, contains multi-core metal oxygen clusters, is connected with ligands to form various three-dimensional hole cage structures such as octahedrons and tetrahedrons, and has the pore channel size of 0.1-1 nm.
2. The metal organic framework material has excellent thermal stability and chemical stability, and can stably exist in water and various organic solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-diethylacetamide, acetonitrile, ethanol, methanol, dimethyl sulfoxide, dioxane, tetrahydrofuran and the like.
3. The metal organic framework material has large specific surface area which is 4000m2More than g, the thermal conductivity coefficient is lower than 0.01 w/m.k, the problem of high thermal conductivity coefficient of the traditional getter is solved, the thermal decomposition temperature is more than 300 ℃, and the thermal stability is good.
4. The metal organic framework material has exposed active sites such as nitrogen atoms, can form strong interaction with nitrogen, oxygen, ammonia gas, carbon dioxide, water vapor and the like, has good adsorption capacity on gas, can replace the traditional getter to be applied to the vacuum heat insulation plate, and can replace the traditional polyurethane to be used as a refrigerator heat insulation material, so that the power consumption of a refrigerator can be reduced to 40-60% of the original power consumption.
Detailed Description
Example 1:
m is Zr, L is 2',5' -dimethoxy- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid, x is 6. The synthesis method of the microporous metal organic framework material comprises the following steps:
(1) zr-containing metal salt zirconium nitrate and 2',5' -dimethoxy- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid are mixed according to the weight ratio of 1: 1, mixing and dissolving in water to prepare a solution;
(2) adding o-methylbenzoic acid into the aqueous solution and uniformly stirring, wherein the ratio of 2',5' -dimethoxy- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid to o-methylbenzoic acid is 1: 1;
(3) adding hydrochloric acid accounting for 1% of the total volume of the solution into the solution, uniformly stirring, putting into a closed hydrothermal kettle, reacting at a constant temperature of 150 ℃ for 2 days, naturally cooling to room temperature, performing centrifugal separation, and cleaning to obtain the microporous metal organic framework material.
The structure and performance of the product are characterized and confirmed by methods such as single crystal X-ray diffraction, element analysis, infrared spectrum, BET specific surface analysis, thermal analysis and the like, the obtained metal organic framework material belongs to a cubic system, the space group is Fm-3m, and a hexanuclear metal oxygen cluster is taken as a node and an organic ligand 2',5' -dimethoxy- [1,1':4',1' -terphenyl]The 4,4' -dicarboxylic acid is connected to form a space network and contains octahedral and tetrahedral two-hole cage structures, wherein the diameter of the octahedral hole cage is
The diameter of the tetrahedral pore cage is
The material has particle size of 50-200nm and specific surface area greater than 5000m
2The thermal conductivity coefficient is lower than 0.01 w/m.k, the thermal decomposition temperature is higher than 350 ℃, and the getter has good adsorption capacity on nitrogen, oxygen, ammonia, carbon dioxide, water vapor and the like and can be used as a getter in a vacuum insulation board.
Example 2:
m is Yb, L is [2,2 '-bipyridine ] -5,5' -dicarboxylic acid, and x is 12. The synthesis method of the microporous metal organic framework material comprises the following steps:
(1) yb-containing metal salt ytterbium chloride and [2,2 '-bipyridyl ] -5,5' -dicarboxylic acid are mixed according to the proportion of 1: 4, mixing and dissolving in N, N-dimethylacetamide to prepare a solution;
(2) adding o-bromobenzoic acid into the solution and stirring uniformly, wherein the ratio of 2',5' -dimethoxy- [1,1':4',1 '-terphenyl ] -4,4' -dicarboxylic acid to o-bromobenzoic acid is 1: 1;
(3) adding tetrafluoroboric acid accounting for 6 percent of the total volume of the solution into the solution, uniformly stirring, putting the mixture into a closed hydrothermal kettle, reacting at a constant temperature of 150 ℃ for 8 days, naturally cooling to room temperature, performing centrifugal separation, and cleaning to obtain the microporous metal organic framework material.
The structure and performance of the product are characterized and confirmed by methods such as single crystal X-ray diffraction, element analysis, infrared spectrum, BET specific surface analysis, thermal analysis and the like, the obtained metal organic framework material belongs to a cubic system, the space group is Fm-3m, and a trinuclear metal oxygen cluster is taken as a node and an organic ligand [2,2' -bipyridine ]]The connection of the 5,5' -dicarboxylic acid forms a space network, the particle size of the material is 100-500nm, and the specific surface area is more than 4000m2The thermal conductivity coefficient is lower than 0.01 w/m.k, the thermal decomposition temperature is higher than 380 ℃, and the ligand contains nitrogen atoms as active sites, so that the interaction with nitrogen, oxygen, ammonia, carbon dioxide and water vapor can be enhanced, the gas adsorption capacity is excellent, and the getter can be used as a getter in a vacuum insulation board.
Example 3:
m is Ti, L is 3, 5-diethoxyterephthalic acid, and x is 6. The synthesis method of the microporous metal organic framework material comprises the following steps:
(1) mixing metal salt titanium nitrate containing Ti and 3, 5-diethoxy terephthalic acid according to the weight ratio of 1: 2 is mixed and dissolved in a mixed solvent of ethanol and N, N-dimethylformamide to prepare a solution;
(2) adding o-fluorobenzoic acid into the solution and stirring uniformly, wherein the ratio of the 3, 5-diethoxyterephthalic acid to the o-fluorobenzoic acid is 1: 1;
(3) adding nitric acid with the volume being 2% of the total volume of the solution into the solution, uniformly stirring, putting the solution into a closed hydrothermal kettle, reacting for 4 days at a constant temperature of 130 ℃, naturally cooling to room temperature, performing centrifugal separation, and cleaning to obtain the microporous metal organic framework material.
By passingThe structure and performance of the product are characterized and confirmed by methods such as single crystal X-ray diffraction, element analysis, infrared spectrum, BET specific surface analysis, thermal analysis and the like, the obtained metal organic framework material belongs to a cubic crystal system, the space group is Fm-3m, a hexanuclear metal oxygen cluster is used as a node to be connected with organic ligand 3, 5-diethoxy terephthalic acid to form a space network, the particle size of the material is 50-400nm, and the specific surface area is more than 5000m2The thermal conductivity coefficient is lower than 0.01 w/m.k, the thermal decomposition temperature is higher than 320 ℃, and the getter has excellent gas adsorption capacity on nitrogen, oxygen, ammonia, carbon dioxide and water vapor and can be used as a getter in a vacuum insulation board.