CN106905539A - Metal organic frame containing energy and preparation method thereof - Google Patents
Metal organic frame containing energy and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- 239000000126 substance Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000012621 metal-organic framework Substances 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 159000000009 barium salts Chemical class 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012046 mixed solvent Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910001626 barium chloride Inorganic materials 0.000 claims description 6
- 238000004729 solvothermal method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- -1 tetrazolium triazoles Chemical class 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005474 detonation Methods 0.000 abstract description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002360 explosive Substances 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 239000003380 propellant Substances 0.000 abstract description 4
- 239000003721 gunpowder Substances 0.000 abstract description 3
- 229910001422 barium ion Inorganic materials 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 238000007789 sealing Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LJDAWFIXFDMQRB-UHFFFAOYSA-N 5-[5-(2h-tetrazol-5-yl)-2h-triazol-4-yl]-2h-tetrazole Chemical compound N1N=NC(C=2C(=NNN=2)C2=NNN=N2)=N1 LJDAWFIXFDMQRB-UHFFFAOYSA-N 0.000 description 1
- 206010015535 Euphoric mood Diseases 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010626 work up procedure 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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Abstract
It is [Ba (HBTT) (H the invention discloses a kind of chemical formula2O)4]n[Ba3(BTT)2(H2O)9]nContaining can metal organic frame and preparation method thereof.The present invention is using the excellent nitrogen high molecule 4 containing energy, 5 two tetrazolium triazoles are used as the part containing energy, using metal barium ions Ba (II) of strong coordination ability as coordination center, method is obtained using regulation and control pH value of reaction system and is successfully prepared barium metal and 4, two different dimensions of 5 two tetrazolium triazoles are metal organic frame i.e. [Ba (HBTT) (H containing energy of 1D and 3D2O)4]n[Ba3(BTT)2(H2O)9]n, two compounds have good security and detonation property, can have preferable application prospect in high-energy insensitive ammunition as the composition of explosive, gunpowder and propellant.
Description
Technical Field
The invention relates to energetic materials, in particular to energetic materials with a chemical formula of [ Ba (HBTT)) (H2O)4]nAnd [ Ba ]3(BTT)2(H2O)9]nAnd a method for preparing the same.
Background
Energy-containing metal-organic frameworks (EMOFs) are coordination polymers with strong explosion functions developed in recent years, the EMOFs have the double advantages of organic and inorganic compared with common elemental explosives, and the coordination hybridization of energy-containing organic molecules and metal inorganic atoms can be represented in a 1D, 2D or 3D form in space; the high-dimensional structure of the ordered structure determines the ideal physical properties of the materials, namely high density and good mechanical properties, and stable chemical properties, namely good thermal stability, high energy output and low sensitivity; this may provide an entirely new direction for the development of new energetic materials. The compound is an important direction for researching high-energy, reliable, safe and environment-friendly energetic materials at present, and has wide application prospects in the fields of explosives, propellants, pyrotechnic agents and the like. Relatively few energy-containing metal-organic frameworks are reported at present, and particularly, the series of EMOFs with high pause-sensing energy is more rare.
As is well known, the polyazole heterocyclic organic molecules have the characteristics of high nitrogen, low carbon hydrogen, high energy and high density, and the compounds are particularly attractive due to higher positive enthalpy of formation. Thomas M, university of Munich, Germany, in 2016.Work-up by et al reported 4, 5-bitetrazole triazole (4,5-Bis (1H-tetrazol-5-yl) -2H-1,2,3-triazole, H3BTT) and the energy properties of related ionic salts and derivatives thereof, experiments show that H3The nitrogen content of BTT is up to 75.1%, the density is 1.69 g.cm < -3 >, the detonation velocity is 8.36km s < -1 >, and the detonation pressure is 24.8 GPa; impact sensitivity (BAM)2J and friction sensitivity (BAM)240N were found, indicating that the friction sensitivity was much lower than RDX. Therefore, the invention successfully prepares two energetic metal-organic frameworks (Ba (HBTT)) with different dimensions (1D and 3D respectively) of metal barium and 4, 5-bitetrazole triazole by using the excellent high-nitrogen energetic molecule as an energetic ligand and using metal barium ions Ba (II) with strong coordination capacity as a coordination center and adopting a method for regulating and controlling the pH value of a reaction system2O)4]nAnd [ Ba ]3(BTT)2(H2O)9]nThe two-example compound has good safety and detonation performance, can be used as the components of explosives, gunpowder and propellants, and has good application prospect in high-energy insensitive ammunition. At present, the metals barium (Ba) and 4, 5-bitetrazole triazole (H)3BTT) has no published literature for two examples of energetic metal-organic frameworks.
Disclosure of Invention
[ problem to be solved ]
The present invention is to solve the above problems of the prior art and to provide a chemical formula of [ Ba (HBTT)) (H2O)4]nAnd [ Ba ]3(BTT)2(H2O)9]nAnd a method for preparing the same. The method enriches the types of EMOFs, explores the influence rule of the pH value of the reaction solution on the structure of the reaction product, and provides a new idea for a preparation method of a new generation of pause-feeling high-energy energetic material.
[ solution ]
In order to achieve the technical effects, the invention adopts the following technical scheme:
a chemical formula is [ Ba (HBTT)) (H2O)4]nThe energetic metal-organic framework of (a).
A chemical formula is [ Ba (HBTT)) (H2O)4]nThe preparation method of the energy-containing metal-organic framework comprises the following steps:
(1) preparation of the reaction System
Adding a metal barium salt and 4, 5-bitetrazole triazole into a mixed solvent system with a specific ratio, fully stirring to obtain a suspension solution, and dropwise adding an HCl aqueous solution to adjust the pH value of the suspension solution to 4.8-5.2;
(2) solvothermal reaction preparation of energetic metal-organic frameworks
Placing the reaction system obtained in the step (1) in a stainless steel reaction kettle, reacting for 48-72 hours at 140-150 ℃, then cooling to room temperature of 25 ℃ by program cooling, opening the reaction device, filtering, washing and drying to obtain the compound with the chemical formula [ Ba (HBT)) (H2O)4]nContaining an energetic metal-organic framework.
A chemical formula of [ Ba3(BTT)2(H2O)9]nThe energetic metal-organic framework of (a).
A chemical formula of [ Ba3(BTT)2(H2O)9]nThe preparation method of the energy-containing metal-organic framework comprises the following steps:
(1) preparation of the reaction System
Adding metal barium salt and 4, 5-bitetrazole triazole into a mixed solvent system with a specific proportion, fully stirring to obtain a suspension solution, and dropwise adding NaOH aqueous solution to adjust the pH value of the suspension solution to 8.7-9.2;
(2) solvothermal reaction preparation of energetic metal-organic frameworks
Placing the reaction system obtained in the step (1) in a stainless steel reaction kettle, reacting for 48-72 hours at 140-150 ℃, then cooling to room temperature of 25 ℃ by program cooling, opening a reaction device, filtering, washing and drying to obtain the compound [ Ba ] with the chemical formula3(BTT)2(H2O)9]nContaining an energetic metal-organic framework.
According to a further technical scheme of the invention, in the preparation method of the two substances, in the step (1), the metal barium salt is Ba (OH)2Or BaCl2。
In a further technical solution of the present invention, in the above two preparation methods, in the step (1), the mixed solvent system with the specific ratio is a mixed solvent system with a volume ratio of 1:1 water and ethanol or a volume ratio of 1:1 water and methanol.
According to a further technical scheme of the invention, in the preparation method of the two substances, in the step (1), the metal barium salt and the 4, 5-bitetrazole triazole are added according to the ratio of the metal barium salt to the 4, 5-bitetrazole triazole being 4.3-5.2: 5.
The invention further adopts the technical scheme that the chemical formula is [ Ba (HBT)) (H2O)4]nIn the step (1) of the preparation method of the energy-containing metal-organic framework, the concentration of the HCl aqueous solution is 0.8-1.2M; the suspension was adjusted to pH 5 by dropwise addition of aqueous HCl.
The invention further adopts the technical scheme that the chemical formula is [ Ba ]3(BTT)2(H2O)9]nIn the step (1) of the preparation method of the energy-containing metal-organic framework, in the step (1), the concentration of the NaOH aqueous solution is 0.8-1.2M; the suspension was adjusted to pH 9 by dropwise addition of aqueous NaOH solution.
According to a further technical scheme of the invention, in the preparation method of the two substances, in the step (2), the procedure cooling is that the temperature is reduced at a cooling speed of 5-10 ℃/h
The present invention will be described in detail below.
The chemical formula of the invention is [ Ba (HBTT)) (H2O)4]nOf an energetic metal-organic framework and a chemical formula of [ Ba3(BTT)2(H2O)9]nThe energetic metal-organic frameworks of (A) are all prepared by using 4, 5-bitetrazole triazole (H)3BTT) as an energetic ligand and barium metal ion Ba (II) as a coordination center, and the two energetic metal-organic frameworks remarkably reduce H3Sensitivity of BTT and significant increase of H3Thermal stability of BTT. The preparation methods of the two energetic metal-organic frameworks are basically the same, and two-dimensional energetic metal-organic frameworks, namely the one-dimensional [ Ba (HBTT) (H), can be successfully prepared only by regulating and controlling the pH value of a reaction system2O)4]nAnd three-dimensional [ Ba3(BTT)2(H2O)9]n。
In the preparation method, the reaction temperature of the reaction system is limited to 140-150 ℃, because the steam pressure in the reaction kettle is suitable for synthesizing the substance in the temperature range. The excessive temperature may cause the pressure in the reaction kettle to be excessive to cause danger. The reaction time is limited to 48-72 h because the reaction time is suitable. Too short a time is not suitable for synthesizing with the substance, and too long a time is wasted. The reaction temperature in step (2) of the preparation method of the invention is preferably 150 ℃, and the reaction time is preferably 72 h. The temperature reduction of the program is required to be slow, the substance is in a dissolved state at high temperature and high pressure, and the slow temperature reduction rate is only suitable for the generation of target substance crystals.
The invention can see the metal barium and H in the chemical formula through the chemical formula of the material3The BTT ratio is about 1:1, and if a certain reactant is excessive, a substance cannot be synthesized or is wasted; therefore, it is preferable to select the amount of the raw material in a range where the ratio of the amount of the raw material to the amount of the raw material should be about 1.
In addition, the polarity, the related solubility and the pressure generated at high temperature in the mixed solvent system with a specific proportion are just suitable for the synthesis of the target substance, and the synthesis process of the metal organic framework is a process of dissolving and then precipitating. The mixed solvent requires suitable high temperature reaction conditions for the reactants. If a mixed solvent system in a specific ratio is not used, synthesis failure may result.
It can be seen that the parameters of each step in the preparation method of the present invention are strictly defined to obtain a product with good quality.
Compared with the prior art, the invention has the following beneficial effects:
the two energetic metal-organic frameworks have good safety and detonation performance, can be used as components of explosives, gunpowder and propellants, and have good application prospects in high-energy insensitive ammunition. The preparation method has the advantages of good process repeatability, mild reaction conditions, good safety and high product quality.
Drawings
FIG. 1 shows a chemical formula of [ Ba (HBTT)) (H2O)4]nSchematic diagram of the crystal structure of the energetic metal-organic framework of (a);
FIG. 2 shows a chemical formula of [ Ba ]3(BTT)2(H2O)9]nSchematic diagram of the crystal structure of the energetic metal-organic framework of (a);
FIG. 3 shows a chemical formula of [ Ba (HBTT)) (H2O)4]nThe XRD patterns of the energetic metal-organic framework powder and single crystal diffraction tests;
FIG. 4 shows a chemical formula of [ Ba ]3(BTT)2(H2O)9]nThe XRD patterns of energetic metal-organic framework powders and single crystal diffraction tests.
Detailed Description
The invention will be further elucidated and described with reference to the embodiments of the invention described hereinafter.
First, the chemical formula is [ Ba (HBTT)) (H2O)4]nPreparation of the energetic metal-organic framework:
example 1
(1) Preparing 10ml of a 1:1 water/ethanol mixed solution, and weighing 105mg (0.5mmol) of 4, 5-bitetrazole triazole (H)3BTT) and 79mg (0.46mmol) of Ba (OH)2And transferring the barium salt solution into a mixed solvent, and adding a proper amount of aqueous solution of HCl (1M) into the solution system to adjust the pH value of the barium salt reaction solution system to 5.
(2) Transferring the mixed solution into a 15ml polytetrafluoroethylene reaction inner cylinder, wherein the polytetrafluoroethylene reaction inner cylinders in all the embodiments of the invention are arranged in a stainless steel reaction kettle sleeve, two devices are a set of devices, the stainless steel high-temperature high-pressure reaction kettle is used for sealing, the reaction kettle is placed into a program temperature control oven to react for 72 hours at a constant temperature of 150 ℃, and the reaction temperature is reduced to room temperature at a speed of 5 ℃/h after the reaction is finished.
(3) Opening the reaction kettle after the reaction, filtering the mixture in the inner cylinder, washing the filtered solid matter with a proper amount of absolute ethyl alcohol, and drying at room temperature to obtain the product [ Ba (HBTT) (H) shown in figures 1 and 32O)4]n。
Example 2
(1) 10ml of a 1:1 water/methanol mixed solution was prepared, and 105mg (0.5mmol) of 4, 5-bitetrazolotriazole (H) was weighed3BTT) and 79mg (0.46mmol) of Ba (OH)2And transferring the barium salt solution into a mixed solvent, and adding a proper amount of aqueous solution of HCl (1M) into the solution system to adjust the pH value of the barium salt reaction solution system to 5.
(2) Transferring the mixed solution into a 15ml polytetrafluoroethylene reaction inner cylinder, sealing the reaction kettle by using a stainless steel high-temperature high-pressure reaction kettle, putting the reaction kettle into a program temperature control oven, reacting for 72 hours at a constant temperature of 150 ℃, and cooling to room temperature at a speed of 5 ℃/h after the reaction is finished.
(3) Opening the reaction kettle after the reaction, filtering the mixture in the inner cylinder, washing the filtered solid substance with a proper amount of anhydrous methanol, and drying at room temperature to obtain the product [ Ba (HBT)) (H2O)4]n。
Example 3
(1) Preparing 10ml of a 1:1 water/ethanol mixed solution, and weighing 105mg (0.5mmol) of 4, 5-bitetrazole triazole (H)3BTT) and 104.1mg (0.5mmol) of BaCl2Transferring into mixed solvent, dissolvingAnd adding a proper amount of HCl (1M) aqueous solution into the liquid system to adjust the pH value of the barium salt reaction liquid system to 5.
(2) Transferring the mixed solution into a 15ml polytetrafluoroethylene reaction inner cylinder, sealing the reaction kettle by using a stainless steel high-temperature high-pressure reaction kettle, putting the reaction kettle into a program temperature control oven, reacting for 72 hours at a constant temperature of 150 ℃, and cooling to room temperature at a speed of 5 ℃/h after the reaction is finished.
(3) Opening the reaction kettle after the reaction, filtering the mixture in the inner cylinder, washing the filtered solid substance with a proper amount of absolute ethyl alcohol, and drying at room temperature to obtain a product [ Ba (HBT)) (H2O)4]n。
Example 4
(1) 10ml of a 1:1 water/methanol mixed solution was prepared, and 105mg (0.5mmol) of 4, 5-bitetrazolotriazole (H) was weighed3BTT) and 104.1mg (0.5mmol) of BaCl2And transferring the barium salt solution into a mixed solvent, and adding a proper amount of aqueous solution of HCl (1M) into the solution system to adjust the pH value of the barium salt reaction solution system to 5.
(2) Transferring the mixed solution into a 15ml polytetrafluoroethylene reaction inner cylinder, sealing the reaction kettle by using a stainless steel high-temperature high-pressure reaction kettle, putting the reaction kettle into a program temperature control oven, reacting for 72 hours at a constant temperature of 150 ℃, and cooling to room temperature at a speed of 5 ℃/h after the reaction is finished.
(3) Opening the reaction kettle after the reaction, filtering the mixture in the inner cylinder, washing the filtered solid substance with a proper amount of anhydrous methanol, and drying at room temperature to obtain the product [ Ba (HBT)) (H2O)4]n。
II, the chemical formula is [ Ba3(BTT)2(H2O)9]nPreparation of the energetic metal-organic framework
Example 1
(1) Prepare 10ml of the body105mg (0.5mmol) of 4, 5-bitetrazolotriazole (H) was weighed out from a 1:1 water/ethanol mixed solution3BTT) and 79mg (0.46mmol) of Ba (OH)2And transferring the barium salt solution into a mixed solvent, and adding a proper amount of aqueous solution of NaOH (1M) into the solution system to adjust the pH value of the barium salt reaction solution system to 9.
(2) Transferring the mixed solution into a 15ml polytetrafluoroethylene reaction inner cylinder, sealing the reaction kettle by using a stainless steel high-temperature high-pressure reaction kettle, putting the reaction kettle into a program temperature control oven, reacting for 72 hours at a constant temperature of 150 ℃, and cooling to room temperature at a speed of 5 ℃/h after the reaction is finished.
(3) Opening the reaction kettle after the reaction, filtering the mixture in the inner cylinder, washing the filtered solid matter with a proper amount of absolute ethyl alcohol, and drying at room temperature to obtain the product [ Ba ] shown in figure 2 and figure 43(BTT)2(H2O)9]n。
Example 2
(1) 10ml of a 1:1 water/methanol mixed solution was prepared, and 105mg (0.5mmol) of 4, 5-bitetrazolotriazole (H) was weighed3BTT) and 79mg (0.46mmol) of Ba (OH)2And transferring the barium salt solution into a mixed solvent, and adding a proper amount of aqueous solution of NaOH (1M) into the solution system to adjust the pH value of the barium salt reaction solution system to 9.
(2) Transferring the mixed solution into a 15ml polytetrafluoroethylene reaction inner cylinder, sealing the reaction kettle by using a stainless steel high-temperature high-pressure reaction kettle, putting the reaction kettle into a program temperature control oven, reacting for 72 hours at a constant temperature of 150 ℃, and cooling to room temperature at a speed of 5 ℃/h after the reaction is finished.
(3) Opening the reaction kettle after the reaction, filtering the mixture in the inner cylinder, washing the filtered solid matter with a proper amount of anhydrous methanol, and drying at room temperature to obtain the product [ Ba3(BTT)2(H2O)9]n。
Example 3
(1) Preparing 10ml of a 1:1 water/ethanol mixed solution, and weighing 105mg (0.5mmol) of 4, 5-bitetrazole triazole (H)3BTT) and 104.1mg (0.5mmol) of BaCl2And transferring the barium salt solution into a mixed solvent, and adding a proper amount of aqueous solution of NaOH (1M) into the solution system to adjust the pH value of the barium salt reaction solution system to 9.
(2) Transferring the mixed solution into a 15ml polytetrafluoroethylene reaction inner cylinder, sealing the reaction kettle by using a stainless steel high-temperature high-pressure reaction kettle, putting the reaction kettle into a program temperature control oven, reacting for 72 hours at a constant temperature of 150 ℃, and cooling to room temperature at a speed of 5 ℃/h after the reaction is finished.
(3) Opening the reaction kettle after the reaction, filtering the mixture in the inner cylinder, washing the filtered solid matter with a proper amount of absolute ethyl alcohol, and drying at room temperature to obtain the product [ Ba3(BTT)2(H2O)9]n。
Example 4
(1) 10ml of a 1:1 water/methanol mixed solution was prepared, and 105mg (0.5mmol) of 4, 5-bitetrazolotriazole (H) was weighed3BTT) and 104.1mg (0.5mmol) of BaCl2And transferring the barium salt solution into a mixed solvent, and adding a proper amount of aqueous solution of NaOH (1M) into the solution system to adjust the pH value of the barium salt reaction solution system to 9.
(2) Transferring the mixed solution into a 15ml polytetrafluoroethylene reaction inner cylinder, sealing the reaction kettle by using a stainless steel high-temperature high-pressure reaction kettle, putting the reaction kettle into a program temperature control oven, reacting for 72 hours at a constant temperature of 150 ℃, and cooling to room temperature at a speed of 5 ℃/h after the reaction is finished.
(3) Opening the reaction kettle after the reaction, filtering the mixture in the inner cylinder, washing the filtered solid matter with a proper amount of anhydrous methanol, and drying at room temperature to obtain the product [ Ba3(BTT)2(H2O)9]n。
The chemical formula obtained by the invention is [ Ba (HBTT)) (H2O)4]nAnd [ Ba ]3(BTT)2(H2O)9]nThe physicochemical properties of the energetic metal-organic framework of (a) are shown in table 1. The chemical formula obtained by the invention is [ Ba (HBTT)) (H2O)4]nAnd [ Ba ]3(BTT)2(H2O)9]nThe energetic metal-organic framework has better safety performance and detonation performance.
Table 1 shows the chemical formula [ Ba (HBTT)) (H2O)4]nAnd [ Ba ]3(BTT)2(H2O)9]nPhysicochemical properties of the energetic metal-organic framework of
Wherein,ax-ray single crystal diffraction crystal density.bNitrogen content.cThe decomposition temperature.dThe sensitivity to impact.eAnd (4) friction sensitivity.fElectrostatic sensitivity.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (10)
1. A chemical formula is [ Ba (HBTT)) (H2O)4]nThe energetic metal-organic framework of (a).
2. A chemical formula is [ Ba (HBTT)) (H2O)4]nThe preparation method of the energy-containing metal-organic framework is characterized by comprising the following steps:
(1) preparation of the reaction System
Adding a metal barium salt and 4, 5-bitetrazole triazole into a mixed solvent system with a specific ratio, fully stirring to obtain a suspension solution, and dropwise adding an HCl aqueous solution to adjust the pH value of the suspension solution to 4.8-5.2;
(2) solvothermal reaction preparation of energetic metal-organic frameworks
Placing the reaction system obtained in the step (1) in a stainless steel reaction kettle, reacting for 48-72 hours at 140-150 ℃, then cooling to room temperature of 25 ℃ by program cooling, opening the reaction device, filtering, washing and drying to obtain the compound with the chemical formula [ Ba (HBT)) (H2O)4]nContaining an energetic metal-organic framework.
3. A chemical formula of [ Ba3(BTT)2(H2O)9]nThe energetic metal-organic framework of (a).
4. A chemical formula of [ Ba3(BTT)2(H2O)9]nThe preparation method of the energy-containing metal-organic framework is characterized by comprising the following steps:
(1) preparation of the reaction System
Adding metal barium salt and 4, 5-bitetrazole triazole into a mixed solvent system with a specific proportion, fully stirring to obtain a suspension solution, and dropwise adding NaOH aqueous solution to adjust the pH value of the suspension solution to 8.7-9.2;
(2) solvothermal reaction preparation of energetic metal-organic frameworks
Placing the reaction system obtained in the step (1) in a stainless steel reaction kettle, reacting for 48-72 hours at 140-150 ℃, then cooling to room temperature of 25 ℃ by program cooling, opening a reaction device, filtering, washing and drying to obtain the compound [ Ba ] with the chemical formula3(BTT)2(H2O)9]nContaining an energetic metal-organic framework.
5. The production method according to claim 2 or claim 4, characterized in that in step (1), the metallic barium salt is Ba (OH)2Or BaCl2。
6. The production method according to claim 2 or claim 4, characterized in that in the step (1), the mixed solvent system in the specific ratio is a mixed solvent system having a volume ratio of 1:1 water and ethanol or a volume ratio of 1:1 water and methanol.
7. The method according to claim 2 or claim 4, wherein in the step (1), the metallic barium salt and the 4, 5-bitetrazole triazole are added in such an amount that the ratio of the amounts of the metallic barium salt and the 4, 5-bitetrazole triazole is 4.3 to 5.2: 5.
8. The method according to claim 2, wherein in the step (1), the concentration of the aqueous HCl solution is 0.8 to 1.2M; the suspension was adjusted to pH 5 by dropwise addition of aqueous HCl.
9. The method according to claim 4, wherein in the step (1), the concentration of the NaOH aqueous solution is 0.8 to 1.2M; the suspension was adjusted to pH 9 by dropwise addition of aqueous NaOH solution.
10. The preparation method according to claim 2 or claim 4, characterized in that in the step (2), the programmed cooling is programmed cooling at a cooling rate of 5-10 ℃/h.
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