Thermally stable potassium-based energetic mofs, methods of making and using the same

Abstract

This invention provides a heat-resistant potassium-based energetic MOF, its preparation method, and its applications, relating to the field of energetic materials technology. The chemical formula of the heat-resistant potassium-based energetic MOF of this invention is K2C5HN. 11 O2, with a molecular structure of 3-nitro-1 H With pyrazole as the central framework, tetrazolium anion functional groups are attached at positions 1 and 4, respectively, and the charge is balanced by potassium ions. The energetic MOF prepared by this invention achieves synergistic optimization of high initiation performance, high energy density, high safety, and environmental friendliness. The preparation process of this invention does not require high temperature and high pressure, the reaction conditions are mild, the raw materials are readily available, the reaction only takes 3 steps, the operation is simple, the yield is stable, the purity is high, and it is easy to realize industrial scale-up production.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials technology, specifically relating to a heat-resistant potassium-based energetic MOF, its preparation method, and its application. Background Technology

[0002] Initiating explosives are a class of highly sensitive energetic materials capable of rapidly transitioning from combustion to detonation, reliably initiating powerful explosives. They are widely used in civilian blasting, weaponry, and various aerospace initiation devices, serving as a crucial material basis for providing initial ignition energy and supporting the development of cutting-edge equipment. Currently, lead azide and lead stearate remain the most widely used initiating explosives globally. Although lead-based initiating explosives have served in both military and civilian fields for over a century, their inherent drawbacks are becoming increasingly apparent: on the one hand, lead azide has extremely high sensitivity, making it highly prone to causing safety accidents; on the other hand, the heavy metal lead released throughout the life cycle of lead-based materials can severely damage the human central nervous system and cardiovascular system, causing persistent environmental pollution. With the deepening of global environmental protection concepts, traditional lead-based initiating explosives can no longer meet the green requirements of modern military and industrial applications. Therefore, developing green, lead-free, safe, and efficient new initiating explosives has become the most urgent and core research topic in the field of energetic materials.

[0003] Potassium-based initiating explosives are highly promising candidates for two main reasons: firstly, potassium ions have positive biological effects on plants and animals; secondly, energetic potassium salts possess the excellent ignition properties of traditional initiating explosives, typically combining good safety with detonation capability. Furthermore, potassium ions have flexible coordination modes, allowing for effective coordination with a variety of organic ligands. More importantly, compared to heavy metal ions such as lead, mercury, and silver, potassium ions are environmentally friendly, possessing enormous potential for the development of green and safe initiating explosives.

[0004] Since 2013, energetic metal-organic framework (E-MOF) materials have gradually emerged and received extensive research. Based on this, in 2016, the JM Shreeve research group at the University of Idaho designed and synthesized a potassium-based energetic MOF—4,4′-bis(dinitromethyl)-3,3′-azofuran potassium. It exhibits high thermal stability (decomposition temperature 229.8℃) and high crystal density (2.039 g / cm³). 3It exhibits excellent detonation performance (detonation velocity 8138 m / s, detonation pressure 30.1 GPa), but its high mechanical sensitivity (IS=2J, FS=20N), cumbersome synthesis process, and expensive raw materials limit its further application. In recent years, researchers have realized that simple synthesis methods are crucial for the commercialization of initiating explosives, and research focus has gradually shifted towards novel initiating explosives with shorter synthesis routes, milder reaction conditions, and simpler operation. For example, in 2023, Professor Cheng Guangbin's research group at Nanjing University of Science and Technology used inexpensive 4,6-dichloro-5-nitropyrimidine as a raw material, reacting it with sodium azide to obtain 5-azido-10-nitro-bis(tetrazozo)[1,5- c :5′,1′- f The sodium pyrimidine salt is then converted into a potassium-based MOF with an extremely low minimum initiation charge via silver salt conversion. This potassium-based MOF exhibits detonation performance comparable to lead azide, but with superior safety (IS=5J, FS=20N), although its thermal decomposition temperature is only 163.6℃. Furthermore, the use of silver nitrate presents challenges due to its high cost and pollution issues. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a heat-resistant potassium-based energetic MOF, its preparation method and application.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention provides a heat-resistant potassium-based energetic MOF having the following structure: .

[0007] This invention also provides a method for preparing the aforementioned heat-resistant potassium-based energetic MOF, characterized by comprising the following steps: S1. Add 3-nitro-4-cyanopyrazole and an equimolar amount of potassium hydroxide to deionized water, then add an acetonitrile solution of cyanoazide, and stir the reaction for a certain period of time; after the reaction is complete, remove the solvent to obtain 5-(3-nitro-4-cyano-1 H -pyrazol-1-yl)tetrazole potassium; S2. Dissolve the potassium 5-(3-nitro-4-cyano-1H-pyrazole-1-yl)tetrazole obtained in step S1 in deionized water, add sodium azide and zinc chloride in sequence, stir well, and heat to 100 ℃. Keep the temperature for a certain time. After the reaction is completed, let it cool to room temperature naturally, adjust the pH of the system to 2~3 with 2 M hydrochloric acid solution, precipitate the precipitate, filter, wash and dry to obtain 5,5'-(3-nitro-1H-pyrazole-1,4-diyl)bis(1H-tetrazole); S3, Take the 5,5'-(3-nitro-1) obtained in step S2... H -pyrazole-1,4-diyl)bis(1 H5,5'-(3-nitro-1-tetraazole) was dissolved in an organic solvent, potassium hydroxide was added, the mixture was stirred for a certain time, the precipitate was collected by filtration and dried to obtain 5,5'-(3-nitro-1-tetraazole). H -pyrazole-1,4-diyl)bis(1 H (-Tetraazole)dipotassium, namely the heat-resistant potassium-based energetic MOF.

[0008] Further, in the preparation method of the heat-resistant potassium-based energetic MOF, the acetonitrile solution of cyanoazide in step S1 is prepared as follows: CNBr is added to anhydrous acetonitrile at 0°C, stirred evenly, and then NaN3 is slowly added. The mixture is stirred at 0-5°C for 4 hours, and the precipitate is removed by filtration to obtain the acetonitrile solution of cyanoazide; wherein each millimole of CNBr is added to 5 mL of anhydrous acetonitrile, and the molar ratio of NaN3, CNBr and 3-nitro-4-cyanopyrazole is 8:2:1.

[0009] Furthermore, in the method for preparing the heat-resistant potassium-based energetic MOF, the stirring reaction time in step S1 is 10-20 h.

[0010] Furthermore, in the method for preparing the heat-resistant potassium-based energetic MOF, the 5-(3-nitro-4-cyano-1-yl)-yl-2 ... H The molar ratio of pyrazol-1-yl)tetrazole potassium, sodium azide, and zinc chloride is 1:1.2~2:1~2, and deionized water is mixed with 5-(3-nitro-4-cyano-1-yl)-(2 ... H The dosage ratio of pyrazole-1-yl)tetrazole potassium is 6~15 mL : 1 g.

[0011] Furthermore, in the method for preparing the heat-resistant potassium-based energetic MOF, the reaction time in step S2 is 5-15 h.

[0012] Furthermore, in the method for preparing the heat-resistant potassium-based energetic MOF, the organic solvent in step S3 is methanol or ethanol.

[0013] Furthermore, in the method for preparing the heat-resistant potassium-based energetic MOF, the organic solvent in step S3 reacts with 5,5'-(3-nitro-1 H -pyrazole-1,4-diyl)bis(1 H The dosage ratio of 5,5'-(3-nitro-1-tetraazole) is 15-30 mL : 1 g; potassium hydroxide and 5,5'-(3-nitro-1-tetraazole) are used. H -pyrazole-1,4-diyl)bis(1 H The molar ratio of 2~2.5 : 1 for 1-tetraazole.

[0014] Furthermore, in the method for preparing the heat-resistant potassium-based energetic MOF, the reaction time in step S3 is 2-6 hours.

[0015] The present invention also provides the application of the aforementioned heat-resistant potassium-based energetic MOF in green initiating explosives.

[0016] Compared with the prior art, the beneficial effects of this invention are as follows:

[0017] (1) The two tetrazolium rings in the heat-resistant potassium-based energetic MOF of the present invention work synergistically with the nitro group and coordination bond, resulting in high detonation capability. 30mg of potassium-based energetic MOF can detonate 100mg of RDX.

[0018] (2) The molecular structure of the heat-resistant potassium-based energetic MOF of the present invention is rich in a tetrazolium ring skeleton with high enthalpy of formation and nitrogen content and a highly stable nitropyrazole ring. It has a high energy level and its detonation velocity (8015m / s) is significantly higher than that of traditional initiating agents (lead azide: 5877m / s).

[0019] (3) The heat-resistant potassium-based energetic MOF of the present invention contains only K, C, H, N and O elements, and does not contain heavy metals such as lead (Pb) and barium (Ba), nor does it contain perchlorate. The entire life cycle from synthesis and use to final disposal is environmentally friendly and conforms to the development trend of green energetic materials in modern times.

[0020] (4) The tetrazolium ring-pyrazole ring-tetrazole ring aromatic conjugated system and the intramolecular hydrogen bonds of O…H and N…H in the heat-resistant potassium-based energetic MOF of the present invention effectively enhance molecular stability. The measured thermal decomposition temperature is 343℃, the impact sensitivity is 4J, and the friction sensitivity is 30N. Compared with the traditional detonator lead azide (decomposition temperature is 315℃, impact sensitivity is 2.5~4J, and friction sensitivity is 0.1~1N), the synthesis and use process is safer.

[0021] (5) The preparation process of the present invention does not require high temperature and high pressure, the reaction conditions are mild, the raw materials are readily available, the reaction only takes 3 steps, the operation is simple, the yield is stable, the purity is high, and it is easy to realize industrial scale-up production. Attached Figure Description

[0022] Figure 1 In Example 1 of this invention, step S1 involves 5-(3-nitro-4-cyano-1- H 1H NMR spectrum of potassium pyrazole-1-yl)tetrazole; Figure 2 In Example 1 of this invention, step S1 involves 5-(3-nitro-4-cyano-1- H C1 NMR spectrum of potassium pyrazole-1-yl)tetrazole; Figure 3 In Example 1 of this invention, step S2 involves 5,5'-(3-nitro-1) H -pyrazole-1,4-diyl)bis(1 H (-Tetraazole) 1H NMR spectrum; Figure 4 In Example 1 of this invention, step S2 involves 5,5'-(3-nitro-1) H -pyrazole-1,4-diyl)bis(1 H (-tetraazole) carbon NMR spectrum; Figure 5 In Example 1 of this invention, step S1 involves 5-(3-nitro-4-cyano-1- H Infrared spectrum of potassium pyrazol-1-yl)tetrazole; Figure 6 In Example 1 of this invention, step S2 involves 5,5'-(3-nitro-1) H -pyrazole-1,4-diyl)bis(1 H Infrared spectrum of -tetraazole; Figure 7 This is a differential scanning calorimeter of a potassium-based MOF in Example 1 of the present invention; Figure 8 This is the 1H NMR spectrum of the potassium-based MOF in Example 1 of the present invention; Figure 9 This is the carbon NMR spectrum of the potassium-based MOF in Example 1 of the present invention; Figure 10 The infrared spectrum of the potassium-based MOF in Example 1 of this invention; Figure 11 This is a schematic diagram of the detonation test device used in this invention, wherein: 1. Detonating cord; 2. Rubber sealing ring; 3. Detonating charge; 4. RDX; 5. Steel ring; 6. Lead plate, the lead plate thickness is 3mm; Figure 12 This is a diagram showing the detonation effect of potassium-based MOF as an initiating explosive in Example 1 of the present invention (30 mg potassium-based MOF detonates 100 mg RDX). Figure 13 This is the single-crystal structure of potassium-based MOF hydrate in Example 1 of the present invention. Detailed Implementation

[0023] The present invention will now be described in further detail with reference to the embodiments.

[0024] Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be construed as limiting the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed in accordance with the techniques or conditions described in the literature in the field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased.

[0025] Example 1 The reaction equation of this invention is as follows: .

[0026] S1. Weigh 4.14 g (0.03 mol) of 3-nitro-4-cyanopyrazole and an equimolar amount of potassium hydroxide (1.68 g, 0.03 mol) and add to 50 mL of deionized water. Stir at room temperature until completely dissolved. Then add an acetonitrile solution of cyanide azide and continue stirring at room temperature for 12 h. After the reaction is complete, remove the solvent by vacuum distillation to obtain 5-(3-nitro-4-cyanopyrazole). H 4.54 g of pyrazole-1-yl)tetrazole potassium, yield 62.0%.

[0027] The acetonitrile solution of cyanoazide was prepared as follows: CNBr (6.36 g, 60 mmol) was added to 300 mL of anhydrous acetonitrile and stirred until homogeneous. Then, NaN3 (15.6 g, 240 mmol) was slowly added and stirred at 0–5 °C for 4 h. The precipitate was removed by filtration to obtain the acetonitrile solution of cyanoazide.

[0028] 1 H NMR (500 MHz, DMSO- d 6): δ = 9.37 ppm. 13 C NMR (125 MHz, DMSO- d 6): δ = 159.70, 155.18, 139.34, 110.80, 90.14 ppm. IR (ATR): ν = 3442, 3251, 3120,2981, 2843, 1611, 1561, 1538, 1452, 1420, 1389, 1338, 1253, 1220, 1158, 1128,1089, 1057, 1032, 1022cm -1 . Elemental analysis calcd. (%) for KC5HN8O2(244.215): C (24.59), H (0.41), N (45.88); found: C (24.52), H (0.43), N(45.82). S2, 5-(3-nitro-4-cyano-1 HPotassium pyrazol-1-yl)tetrazole (4.88 g, 0.02 mol) was dissolved in 30 mL of deionized water and placed in a 150 mL round-bottom flask. Sodium azide (1.95 g, 0.03 mol) and zinc chloride (2.73 g, 0.02 mol) were added sequentially to the solution. After stirring for 30 min, the mixture was heated to 100 °C and maintained at this temperature for 10 h. After the reaction was complete, the system was cooled to room temperature, and the pH was adjusted to 2-3 with 2 M hydrochloric acid solution, resulting in the precipitation of a white precipitate. The precipitate was filtered, washed, and dried to obtain 5,5'-(3-nitro-1-yl)-tetrazole. H -pyrazole-1,4-diyl)bis(1 H 4.30 g of tetrazolium (-tetraazole), yield 86.4%.

[0029] 1 H NMR (500 MHz, DMSO- d 6): δ = 7.33 ppm. 13 C NMR (125 MHz, DMSO- d 6): δ = 158.73, 154.53, 147.34, 135.99, 105.14 ppm; IR (ATR): ν = 3705, 3680, 3306,3268, 3153, 2972, 2864, 2843, 1593, 1536, 1478, 1438, 1366, 1317, 1216, 1178,1113, 1054, 1032 cm -1 ; Elemental analysis calcd. (%) for C5H3N 11 O2 (249.154): C (24.10), H (1.21), N (61.84); found: C (24.12), H (1.20), N (61.82). S3, 0.50 g (2 mmol) of 5,5'-(3-nitro-1 H -pyrazole-1,4-diyl)bis(1 H 5,5'-(3-nitro-1-tetraazole) was dissolved in 10 mL of methanol. Two equivalents of potassium hydroxide (0.23 g, 4 mmol) were added to this solution at 25 °C. The reaction mixture was stirred at room temperature for 5 h. The precipitate was collected by filtration and dried under vacuum to give 5,5'-(3-nitro-1-tetraazole). H -pyrazole-1,4-diyl)bis(1 H 0.54 g of dipotassium tetrazolium (DTT) MOF, yield 83.6%.

[0030] Figure 7 The differential scanning calorimetry (DSC) image of the heat-resistant potassium-based MOF prepared in Example 1 of this invention is shown below. Figure 7 As shown, the test conditions were a nitrogen atmosphere and a heating rate of 5℃ / min. The decomposition peak temperature reached 343℃. There was no melting and heat absorption process before thermal decomposition. The exothermic peak was sharp and narrow, exhibiting significant exothermic characteristics of the detonator.

[0031] Figure 8 The above is the 1H NMR spectrum of the heat-resistant potassium-based MOF prepared in Example 1 of this invention, as shown below. Figure 8 As shown, the 1H NMR spectrum is 1 H NMR (DMSO- d 6): δ 8.58 ppm.

[0032] Figure 9 The image shows the carbon NMR spectrum of the heat-resistant potassium-based MOF prepared in Example 1 of this invention. Figure 9 As shown, the carbon NMR spectrum is 13 C NMR (DMSO- d 6): δ 159.68, 153.30, 151.43, 130.81, 110.80 ppm.

[0033] Figure 10 The infrared spectrum of the heat-resistant potassium-based MOF prepared in Example 1 of this invention is shown below. Figure 10 As shown, IR(ATR): ν 3705, 3680, 3263, 3137, 2972, 2835, 2843, 1543, 1454, 1440, 1397, 1370, 1339,1248, 1127, 1055, 1032, 1018 cm -1 .

[0034] Elemental analysis of K2C5HN 11 O2 (325.335): Measured (calculated) C: 18.42 (18.46)%, H: 0.30 (0.31)%, N: 47.32 (47.36)%.

[0035] The heat-resistant potassium-based MOF prepared in Example 1 was subjected to BAM sensitivity testing. The impact sensitivity was 4J and the friction sensitivity was 30N, which is lower than that of the conventional initiator lead azide (impact sensitivity is 2.5~4J and friction sensitivity is 0.1~1N).

[0036] The heat-resistant potassium-based MOF prepared in Example 1 was used as an initiating explosive. Figure 11The detonation device shown was tested, using 30 mg of detonating explosive to detonate 100 mg of RDX. The results are as follows. Figure 12 As shown, the RDX was successfully detonated, and the diameter of the perforation in the lead plate was 10mm.

[0037] The heat-resistant potassium-based MOF prepared in Example 1 was dissolved in water and cultured as a single crystal. Single-crystal diffraction tests showed that its monohydrate exhibited the following properties. Figure 13 The single-crystal structure shown. Cell parameters: monoclinic system, P 21 / c point group; a = 7.4648 (3) Å, b =23.8561 (8) Å, c = 7.3040 (3) Å, α = 90º, b = 117.952 (1)°, γ = 90º; Cell volume: 1148.96 (8) Å 3 Z = 4; Density: 1.985 g∙cm⁻¹ -3 (170 K).

[0038] Example 2 S1. Weigh 4.14 g (0.03 mol) of 3-nitro-4-cyanopyrazole and an equimolar amount of potassium hydroxide (1.68 g, 0.03 mol) and add to 50 mL of deionized water. Stir at room temperature until completely dissolved. Then add an acetonitrile solution of cyanide azide and continue stirring at room temperature for 10 h. After the reaction is complete, remove the solvent by vacuum distillation to obtain 5-(3-nitro-4-cyanopyrazole). H 4.40 g of pyrazole-1-yl)tetrazole potassium, yield 60.1%.

[0039] The acetonitrile solution of cyanoazide was prepared as follows: CNBr (6.36 g, 60 mmol) was added to 300 mL of anhydrous acetonitrile and stirred until homogeneous. Then, NaN3 (15.6 g, 240 mmol) was slowly added and stirred at 0–5 °C for 4 h. The precipitate was removed by filtration to obtain the acetonitrile solution of cyanoazide.

[0040] S2, 5-(3-nitro-4-cyano-1 HPotassium pyrazol-1-yl)tetrazole (4.88 g, 0.02 mol) was dissolved in 55 mL of deionized water and placed in a 150 mL round-bottom flask. Sodium azide (1.56 g, 0.024 mol) and zinc chloride (4.09 g, 0.03 mol) were added sequentially to the solution. After stirring for 30 min, the mixture was heated to 100 °C and maintained at this temperature for 5 h. After the reaction was complete, the system was cooled to room temperature, and the pH was adjusted to 2-3 with 2 M hydrochloric acid solution, resulting in the precipitation of a white precipitate. The precipitate was filtered, washed, and dried to obtain 5,5'-(3-nitro-1-yl)-tetrazole. H -pyrazole-1,4-diyl)bis(1 H 4.15 g of tetrazolium (-tetraazole), yield 83.3%.

[0041] S3, 0.50 g (2 mmol) of 5,5'-(3-nitro-1 H -pyrazole-1,4-diyl)bis(1 H 5,5'-(3-nitro-1-tetraazole) was dissolved in 7.5 mL of methanol. Two equivalents of potassium hydroxide (0.25 g, 4.4 mmol) were added to this solution at 25 °C. The reaction mixture was stirred at room temperature for 2 h. The resulting precipitate was collected by filtration and dried under vacuum to give 5,5'-(3-nitro-1-tetraazole). H -pyrazole-1,4-diyl)bis(1 H 0.48 g of dipotassium tetrazolium (DTT) MOF, yield 73.8%.

[0042] Example 3 S1. Weigh 4.14 g (0.03 mol) of 3-nitro-4-cyanopyrazole and an equimolar amount of potassium hydroxide (1.68 g, 0.03 mol) and add to 50 mL of deionized water. Stir at room temperature until completely dissolved. Then add an acetonitrile solution of cyanide azide and continue stirring at room temperature for 20 h. After the reaction is complete, remove the solvent by vacuum distillation to obtain 5-(3-nitro-4-cyanopyrazole). H 5.22 g of pyrazole-1-yl)tetrazole potassium, yield 71.2%.

[0043] The acetonitrile solution of cyanoazide was prepared as follows: CNBr (6.36 g, 60 mmol) was added to 300 mL of anhydrous acetonitrile and stirred until homogeneous. Then, NaN3 (15.6 g, 240 mmol) was slowly added and stirred at 0–5 °C for 4 h. The precipitate was removed by filtration to obtain the acetonitrile solution of cyanoazide.

[0044] S2, 5-(3-nitro-4-cyano-1 HPotassium pyrazol-1-yl)tetrazole (4.88 g, 0.02 mol) was dissolved in 73 mL of deionized water and placed in a 150 mL round-bottom flask. Sodium azide (2.60 g, 0.04 mol) and zinc chloride (5.45 g, 0.04 mol) were added sequentially to the solution. After stirring for 30 min, the mixture was heated to 100 °C and maintained at this temperature for 15 h. After the reaction was complete, the system was cooled to room temperature, and the pH was adjusted to 2-3 with 2 M hydrochloric acid solution, resulting in the precipitation of a white precipitate. The precipitate was filtered, washed, and dried to obtain 5,5'-(3-nitro-1-yl)-tetrazole. H -pyrazole-1,4-diyl)bis(1 H 4.28 g of tetrazolium (-tetraazole), yield 85.9%.

[0045] S3, 0.50 g (2 mmol) of 5,5'-(3-nitro-1 H -pyrazole-1,4-diyl)bis(1 H 5,5'-(3-nitro-1-tetraazole) was dissolved in 15 mL of ethanol. Two equivalents of potassium hydroxide (0.28 g, 5 mmol) were added to this solution at 25 °C. The reaction mixture was stirred at room temperature for 6 h. The precipitate was collected by filtration and dried under vacuum to give 5,5'-(3-nitro-1-tetraazole). H -pyrazole-1,4-diyl)bis(1 H 0.51 g of dipotassium tetrazolium (DTT) MOF, yield 78.4%.

[0046] The above embodiments have provided a detailed description of the implementation of the present invention. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention. The above descriptions are merely preferred embodiments of the present invention and do not limit the scope of the present invention. All equivalent structural changes made based on the content of this specification are included within the scope of the present invention.

Claims

1. A heat-resistant potassium-based energetic MOF, characterized in that, It has the following structure: 。 2. The method for preparing the heat-resistant potassium-based energetic MOF according to claim 1, characterized in that, Includes the following steps: S1. Add 3-nitro-4-cyanopyrazole and an equimolar amount of potassium hydroxide to deionized water, then add an acetonitrile solution of cyanoazide, and stir the reaction for a certain period of time; after the reaction is complete, remove the solvent to obtain 5-(3-nitro-4-cyano-1 H -pyrazol-1-yl)tetrazole potassium; S2. Dissolve the potassium 5-(3-nitro-4-cyano-1H-pyrazole-1-yl)tetrazole obtained in step S1 in deionized water, add sodium azide and zinc chloride in sequence, stir well, and heat to 100 ℃. Keep the temperature for a certain time. After the reaction is completed, let it cool to room temperature naturally, adjust the pH of the system to 2~3 with 2 M hydrochloric acid solution, precipitate the precipitate, filter, wash and dry to obtain 5,5'-(3-nitro-1H-pyrazole-1,4-diyl)bis(1H-tetrazole); S3, Take the 5,5'-(3-nitro-1) obtained in step S2... H -pyrazole-1,4-diyl)bis(1 H 5,5'-(3-nitro-1-tetraazole) was dissolved in an organic solvent, potassium hydroxide was added, the mixture was stirred for a certain time, the precipitate was collected by filtration and dried to obtain 5,5'-(3-nitro-1-tetraazole). H -pyrazole-1,4-diyl)bis(1 H (-Tetraazole)dipotassium, namely the heat-resistant potassium-based energetic MOF.

3. The method for preparing a heat-resistant potassium-based energetic MOF according to claim 2, characterized in that, The acetonitrile solution of cyanoazide described in step S1 is prepared as follows: CNBr is added to anhydrous acetonitrile at 0°C and stirred until homogeneous. Then, NaN3 is slowly added and stirred at 0–5°C for 4 hours. The precipitate is removed by filtration to obtain the acetonitrile solution of cyanoazide. Each millimole of CNBr is added to 5 mL of anhydrous acetonitrile, and the molar ratio of NaN3, CNBr, and 3-nitro-4-cyanopyrazole is 8:2:

1.

4. The method for preparing a heat-resistant potassium-based energetic MOF according to claim 2, characterized in that, The stirring reaction time in step S1 is 10-20 h.

5. The method for preparing a heat-resistant potassium-based energetic MOF according to claim 2, characterized in that, The 5-(3-nitro-4-cyano-1) mentioned in step S2 H The molar ratio of pyrazol-1-yl)tetrazole potassium, sodium azide, and zinc chloride is 1:1.2~2:1~2, and deionized water is mixed with 5-(3-nitro-4-cyano-1-yl)-(2 ... H The dosage ratio of pyrazole-1-yl)tetrazole potassium is 6~15 mL : 1 g.

6. The method for preparing a heat-resistant potassium-based energetic MOF according to claim 2, characterized in that, The reaction time in step S2 is 5 to 15 hours.

7. The method for preparing a heat-resistant potassium-based energetic MOF according to claim 2, characterized in that, The organic solvent mentioned in step S3 is methanol or ethanol.

8. The method for preparing a heat-resistant potassium-based energetic MOF according to claim 2, characterized in that, The organic solvent described in step S3 and 5,5'-(3-nitro-1 H -pyrazole-1,4-diyl)bis(1 H The dosage ratio of 5,5'-(3-nitro-1-tetraazole) is 15-30 mL : 1 g; potassium hydroxide and 5,5'-(3-nitro-1-tetraazole) are used. H -pyrazole-1,4-diyl)bis(1 H The molar ratio of 2~2.5 : 1 for 1-tetraazole.

9. The method for preparing a heat-resistant potassium-based energetic MOF according to claim 2, characterized in that, The reaction time in step S3 is 2 to 6 hours.

10. The application of the heat-resistant potassium-based energetic MOF as described in claim 1 in green initiating explosives.

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