Preparation of [ Ba (BTO) (H)2O)]nHectogram solution crystallization method of barium-based energetic metal organic framework
阅读说明：本技术 制备[Ba(BTO)(H2O)]n的钡基含能金属有机框架的百克量级溶液结晶方法 (Preparation of [ Ba (BTO) (H)2O)]nHectogram solution crystallization method of barium-based energetic metal organic framework ) 是由 张祺 陈东 李洪珍 于 2020-10-30 设计创作，主要内容包括：本发明公开了一种制备[Ba(BTO)(H-2O)]-n的钡基含能金属有机框架的百克量级溶液结晶方法,包括以下步骤：步骤1：酸性5,5’-联四唑-1,1’-二氧羟胺盐母液的制备；步骤2：无机金属钡盐母液的制备；步骤3：将两种母液通过蠕动泵进行混合,并在一定反应条件下进行[Ba(BTO)(H-2O)]-n的溶析结晶和晶体陈化；步骤4：[Ba(BTO)(H-2O)]-n晶体的后处理。本发明利用溶液酸性调节使得含能配体5,5’-联四唑-1,1’-二氧负离子能够快速与钡离子形成金属有机框架材料,通过适当的陈化得到高质量的钡基金属有机框架晶体,该制备技术可以实现钡基金属有机框架晶体百克量级的快速制备。(The invention discloses a method for preparing [ Ba (BTO)) (H 2 O)] n The crystallization method of hectogram-level solution of barium-based energetic metal organic framework comprises the following steps: step 1: preparing mother liquor of acidic 5,5 '-bitetrazole-1, 1' -dioxy hydroxylamine salt; step 2: preparing inorganic metal barium salt mother liquor; and step 3: mixing the two mother liquors by a peristaltic pump, and performing [ Ba (BTO) (H) under certain reaction conditions 2 O)] n The dissolution crystallization and the crystal aging; and 4, step 4: [ Ba (BTO)) (H 2 O)] n And (4) carrying out post-treatment on the crystals. According to the invention, the energetic ligand 5,5 '-bitetrazole-1, 1' -dioxygen anion can rapidly form a metal-organic framework material with barium ions by utilizing solution acidity adjustment, and a high-quality barium-based metal-organic framework crystal is obtained through appropriate aging.)
1. Preparation of [ Ba (BTO) (H)2O)]nThe method for crystallizing the barium-based energetic metal organic framework in hectogram solution is characterized in that BTO in the formula is 5,5 '-bitetrazole-1, 1' -dioxygen anion ligand, and the solution crystallization method and the crystal aging method are used for preparing the energetic metal organic framework material [ Ba (BTO) (H)2O)]n。
2. Preparation of [ Ba (BTO) (H) according to claim 12O)]nThe crystallization method of the barium-based energetic metal organic framework solution with hectogram scale is characterized in that the solution crystallization method and the crystal aging method comprise the following steps:
step 1: preparation of mother liquor of acidic 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt
Weighing a certain amount of 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt, transferring the 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt into a clean flask, and adding deionized water into the flask to form turbid liquid; heating the turbid liquid to a certain temperature and continuously stirring until the 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt is completely dissolved, and adding a certain amount of hydrochloric acid to adjust the pH value to form a mother liquid of the acidic 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt;
step 2: preparation of mother liquor of inorganic metal barium salt
Weighing a certain amount of inorganic metal barium salt, transferring the inorganic metal barium salt into a clean weighing bottle, adding deionized water into the weighing bottle, and continuously stirring at room temperature until the inorganic metal barium salt is completely dissolved;
and step 3: mother liquor mixing and crystal aging
Slowly dropwise adding the completely dissolved inorganic metal barium salt solution into an acidic 5,5 '-bitetrazole-1, 1' -dioxyammonium hydroxide salt solution through a peristaltic pump, controlling the flow rate and keeping the solution constant in the process, generating a large amount of white precipitates along with the addition of the inorganic metal barium salt mother solution, and performing constant temperature crystal aging for a certain time after the inorganic metal barium salt is dropwise added into the solution;
and 4, step 4: product post-treatment
After the reaction is finished, cooling the reaction turbid liquid to room temperature, and performing suction filtration by using a vacuum pump to obtain white powder, namely [ Ba (BTO)) (H2O)]nThe wet product is dried in a vacuum oven and finally a hectogram product is obtained.
3. Preparation of [ Ba (BTO) (H) according to claim 12O)]nThe crystallization method of hectogram-level solution of barium-based energetic metal organic framework is characterized in that the concentration of 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt in the acidic mother liquor of the step 1 is 0.5-2mol/L-1。
4. Preparation of [ Ba (BTO) (H) according to claim 12O)]nThe crystallization method of barium-based energy-containing metal organic framework solution in hectogram scale, characterized in that, the pH of the mother liquor of acidic 5,5 '-bitetrazole-1, 1' -dioxyammonium salt in the step 1 is in the range of 4-6.
5. Preparation of [ Ba (BTO) (H) according to claim 12O)]nThe crystallization method of the hectogram-level solution of the barium-based energetic metal organic framework is characterized in that in the step 2, the types of the inorganic metal barium salt are barium chloride and barium nitrate.
6. Preparation of [ Ba (BTO) (H) according to claim 12O)]nThe crystallization method of the barium-based energetic metal organic framework solution is characterized in that the concentration of inorganic metal barium salt in the step 2 is 0.5-2mol/L-1And ensure the amount of barium ion substance and 5,5 '-bistetrazole-1, 1' -dioxygen hydroxyl ammonium salt in the mother liquor of the acidic 5,5 '-bistetrazole-1, 1' -dioxygen hydroxyl ammonium saltThe amount of tetrazole-1, 1' -dioxygen anion substance is equal.
7. Preparation of [ Ba (BTO) (H) according to claim 12O)]nThe crystallization method of the hectogram-level solution of the barium-based energetic metal organic framework is characterized in that in the step 3, the aging temperature is 60-80 ℃, and the aging time is 1-3 hours.
Technical Field
The invention relates to the technical field of novel energetic materials, in particular to a method for preparing [ Ba (BTO)) (H2O)]nThe barium-based energy-containing metal organic framework crystallization method is a hectogram solution crystallization method.
Background
The bistetrazole derivative well inherits the advantages of the tetrazole derivative, further improves the stability of a system, and provides multiple sites for subsequent modification. Compared with a single tetrazole ring, the multi-dimensional porous energetic MOFs has more coordination combination forms, and more possibilities are provided for constructing the multi-dimensional porous energetic MOFs. The bicyclic or polycyclic tetrazole compounds are expected to be widely used in novel explosive rocket propellants, gas generating agents, low-smoke or smokeless fireworks due to a series of excellent properties such as a large amount of tetrazole rings, high nitrogen content, and most of gas generation, namely N2, and a plurality of novel bicyclic or polycyclic tetrazole compounds are synthesized in recent years, and application research is carried out on some of the compounds with good performance. Meanwhile, few energetic metal-organic frameworks based on bitetrazole have been reported so far. It is much more likely to develop a few specific applications. From the current research progress, energetic MOFs based on bitetrazole have shown great advantages in high-density, high-energy, insensitive, environment-friendly and green energetic materials. Because of the urgent need for new energetic materials, the research on energetic coordination polymers of bitetrazole is very meaningful and essential.
A series of energetic salts based on 5,5 '-bitetrazole-1, 1' -dioxygen anion are a very excellent group of energetic compounds of the bitetrazole type, and among them, 5 '-bitetrazole-1, 1' -dioxygen ammonium salt is widely noted for its high safety and high energy density. However, no report is found on the large-scale synthesis process of the energetic metal-organic framework material based on the 5,5 '-bitetrazole-1, 1' -dioxygen anion at present. The preparation of the barium-based energetic metal-organic framework material based on the 5,5 '-bitetrazole-1, 1' -dioxygen anion is realized by using a simple solution crystallization method, and the preparation technology provides a solid material foundation for the application and development of the energetic metal-organic framework material of the 5,5 '-bitetrazole-1, 1' -dioxygen anion.
Disclosure of Invention
The object of the present invention is to provide a process for the preparation of [ Ba (BTO) (H)2O)]nThe invention relates to a hectogram solution crystallization method of a barium-based energetic metal organic framework, which utilizes solution acidity adjustment to enable energetic ligand 5,5 '-bitetrazole-1, 1' -dioxygen anion to rapidly form a metal organic framework material with barium ions, and the metal organic framework material is prepared byThe barium-based metal organic framework crystal with high quality is obtained by proper aging, and the preparation technology can realize the hectogram-level rapid preparation of the barium-based metal organic framework crystal.
In order to achieve the purpose, the invention adopts the following technical scheme:
preparation of [ Ba (BTO) (H)2O)]nIn the method, BTO is a 5,5 '-bitetrazole-1, 1' -dioxygen anion ligand, and the method uses a solution crystallization method and a crystal aging method to prepare the hectogram energy-containing metal organic framework material [ Ba (BTO) (H)2O)]n。
The solution crystallization method and the crystal aging method include the steps of:
step 1: preparation of mother liquor of acidic 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt
Weighing a certain amount of 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt, transferring the 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt into a clean flask, and adding deionized water into the flask to form turbid liquid; heating the turbid liquid to a certain temperature and continuously stirring until the 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt is completely dissolved, and adding a certain amount of hydrochloric acid to adjust the pH value to form a mother liquid of the acidic 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt;
step 2: preparation of mother liquor of inorganic metal barium salt
Weighing a certain amount of inorganic metal barium salt, transferring the inorganic metal barium salt into a clean weighing bottle, adding deionized water into the weighing bottle, and continuously stirring at room temperature until the inorganic metal barium salt is completely dissolved;
and step 3: mother liquor mixing and crystal aging
Slowly dropwise adding the completely dissolved inorganic metal barium salt solution into an acidic 5,5 '-bitetrazole-1, 1' -dioxyammonium hydroxide salt solution through a peristaltic pump, controlling the flow rate and keeping the solution constant in the process, generating a large amount of white precipitates along with the addition of the inorganic metal barium salt mother solution, and performing constant temperature crystal aging for a certain time after the inorganic metal barium salt is dropwise added into the solution;
and 4, step 4: product post-treatment
After the reaction is finished, cooling the reaction turbid liquid to the roomFiltering with vacuum pump to obtain white powder [ Ba (BTO) (H)2O)]nThe wet product is dried in a vacuum oven and finally a hectogram product is obtained.
The concentration of the 5,5 '-bitetrazole-1, 1' -dioxygen hydroxyl ammonium salt in the acid mother liquor of the step 1 is 0.5-2mol/L-1。
The pH of the mother liquor of the acidic 5,5 '-bitetrazole-1, 1' -dioxyammonium salt in step 1 is in the range of 4 to 6.
In the step 2, the inorganic metal barium salt is barium chloride and barium nitrate.
The concentration of the inorganic metal barium salt in the step 2 is 0.5-2mol/L-1And ensures that the amount of barium ion substances is equal to the amount of 5,5 '-bitetrazole-1, 1' -dioxygen anion substances in the acidic 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt mother liquor.
In the step 3, the aging temperature is 60-80 ℃, and the aging time is 1-3 hours.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the energetic ligand 5,5 '-bitetrazole-1, 1' -dioxygen anion can rapidly form a metal-organic framework material with barium ions by utilizing solution acidity adjustment, and a high-quality barium-based metal-organic framework crystal is obtained through appropriate aging.
Drawings
FIG. 1; barium-based energetic metal organic framework materials [ Ba (BTO)) (H2O)]nThermal decomposition temperature diagram of
FIG. 2: barium-based energetic metal organic framework materials [ Ba (BTO)) (H2O)]nPowder XRD test pattern of
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, other embodiments used by those skilled in the art without any creative effort belong to the protection scope of the present invention.
Example 1
Step 1: preparation of mother liquor of acidic 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt
118.0g of 5,5 '-bistetrazole-1, 1' -dioxyhydroxylammonium salt was weighed out and transferred into a clean flask, to which 500ml of deionized water was added to form a turbid liquid. The turbid solution was heated to 60 ℃ with constant stirring until the 5,5 '-bitetrazole-1, 1' -dioxyammonium salt was completely dissolved, and concentrated hydrochloric acid (36.5% by weight) was added thereto to adjust the pH to 5, thereby forming a mother liquor of acidic 5,5 '-bitetrazole-1, 1' -dioxyammonium salt.
Step 2: preparation of mother liquor of inorganic metal barium salt
104.1g of barium chloride is weighed and transferred into a clean weighing bottle, 500ml of deionized water is added into the weighing bottle, and the mixture is continuously stirred at room temperature until the barium chloride is completely dissolved to form a barium chloride mother liquor.
And step 3: mother liquor mixing and crystal aging
The completely dissolved barium chloride solution was slowly added dropwise into the acidic 5,5 '-bitetrazole-1, 1' -dioxyammonium salt solution kept at 60 ℃ by a peristaltic pump, the flow rate was controlled at 10ml/min, the solution temperature was maintained at 60 ℃ during the process, and the solution was rapidly stirred at a rate of 800r/min, and it was seen that white precipitates appeared immediately after the barium chloride solution was added dropwise. After the dripping of the barium chloride solution, the temperature is kept constant at 60 ℃, and the crystal aging is carried out for 1 hour.
And 4, step 4: product post-treatment
After the reaction is finished, cooling the reaction turbid liquid to room temperature, performing suction filtration by using a vacuum pump to obtain white powder, namely [ Ba (BTO) (H2O) ] n, drying the wet product by using a vacuum oven, and finally obtaining a hectogram-level product with the yield of 99%.
The hectogram product was thermally analyzed by differential thermogravimetry, and the results are shown in fig. 1. The hectogram-magnitude product has good thermal stability, and an obvious exothermic peak and weight loss curve appear near 375 ℃. In addition, the compound is subjected to a powder XRD test, as shown in figure 2, the XRD spectrum has a high-quality diffraction line, the hectogram-level product has very good crystal quality, and the line is in good agreement with theoretical simulation, so that the compound is proved to be a high-purity crystalline product.
Example 2
Step 1: preparation of mother liquor of acidic 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt
118.0g of 5,5 '-bistetrazole-1, 1' -dioxyhydroxylammonium salt was weighed out and transferred into a clean flask, into which 1000ml of deionized water was added to form a turbid liquid. The turbid solution was heated to 60 ℃ with constant stirring until the 5,5 '-bitetrazole-1, 1' -dioxyammonium salt was completely dissolved, and concentrated hydrochloric acid (36.5% by weight) was added thereto to adjust the pH to 4, to form a mother liquor of acidic 5,5 '-bitetrazole-1, 1' -dioxyammonium salt.
Step 2: preparation of mother liquor of inorganic metal barium salt
104.1g of barium chloride is weighed and transferred into a clean weighing bottle, 1000ml of deionized water is added into the weighing bottle, and the mixture is continuously stirred at room temperature until the barium chloride is completely dissolved to form a barium chloride mother liquor.
And step 3: mother liquor mixing and crystal aging
The completely dissolved barium chloride solution was slowly added dropwise into the acidic 5,5 '-bitetrazole-1, 1' -dioxyammonium salt solution kept at 60 ℃ by a peristaltic pump, the flow rate was controlled at 20ml/min, the solution temperature was maintained at 60 ℃ during the process, and the solution was rapidly stirred at a rate of 800r/min, and it was seen that a white precipitate appeared immediately after the barium chloride solution was added dropwise. After the barium chloride solution was dropped, stirring was continued for 1 hour.
The completely dissolved inorganic metal barium salt solution is slowly dripped into the acidic 5,5 '-bitetrazole-1, 1' -dioxygen hydroxyl ammonium salt solution through a peristaltic pump, the flow rate is controlled, the solution is kept at a constant temperature in the process, and a large amount of white precipitate is generated along with the addition of the inorganic metal barium salt mother solution. After the dripping of the barium chloride solution, the temperature is kept constant at 60 ℃, and the crystal aging is carried out for 1 hour.
And 4, step 4: product post-treatment
After the reaction is finished, cooling the reaction turbid liquid to room temperature, and performing suction filtration by using a vacuum pump to obtain white powder, namely [ Ba (BTO)) (H2O)]nThe wet product was dried in a vacuum oven to give a hectogram product with a yield of 99％。
Example 3
Step 1: preparation of mother liquor of acidic 5,5 '-bitetrazole-1, 1' -dioxygen hydroxylammonium salt
118.0g of 5,5 '-bistetrazole-1, 1' -dioxyhydroxylammonium salt are weighed out and transferred into a clean flask, and 500ml of deionized water are added to the weighing flask to form a turbid liquid. The turbid solution was heated to 60 ℃ with constant stirring until the 5,5 '-bitetrazole-1, 1' -dioxyammonium salt was completely dissolved, and concentrated hydrochloric acid (36.5% by weight) was added thereto to adjust the pH to 4, to form a mother liquor of acidic 5,5 '-bitetrazole-1, 1' -dioxyammonium salt.
Step 2: preparation of mother liquor of inorganic metal barium salt
130.7g of barium nitrate is weighed and transferred into a clean weighing bottle, 500ml of deionized water is added into the weighing bottle, and the mixture is continuously stirred at room temperature until the barium nitrate mother liquor is completely dissolved to form the barium nitrate mother liquor.
And step 3: mother liquor mixing and crystal aging
The completely dissolved barium nitrate solution is slowly dripped into the acidic 5,5 '-bitetrazole-1, 1' -dioxyammonium salt solution which is kept at the temperature of 60 ℃ by a peristaltic pump, the flow rate is controlled at 10ml/min, the solution temperature is kept at 60 ℃ in the process, and the solution is rapidly stirred at the speed of 800r/min, so that white precipitates can be seen just after the barium nitrate solution is dripped. After the barium nitrate solution was dropped, stirring was continued for 1 hour.
And 4, step 4: product post-treatment
After the reaction is finished, cooling the reaction turbid liquid to room temperature, and performing suction filtration by using a vacuum pump to obtain white powder, namely [ Ba (BTO)) (H2O)]nThe wet product was dried in a vacuum oven and finally yielded a hectogram product with a yield of 98%.
The invention relates to a method for preparing a barium-based energetic metal organic framework material [ Ba (BTO) (H) by using a simple solution crystallization method2O)]nA hectogram-level green rapid preparation method. The method only uses water as a solvent, and has good environmental friendliness. In addition, the preparation method can obtain the product with stoichiometric equivalent, greatly improves the atom utilization rate, almost has no raw material emission to the environment, and greatly reduces the three-waste emission. The invention aims at barium-based energetic metal organic framework material [ Ba (BTO) (H)2O)]nA reliable, simple and convenient rapid green preparation method suitable for amplification is designed and developed.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.