CN114105719B - Core-shell structure carbon-based copper azide composite energetic material and preparation method thereof - Google Patents
Core-shell structure carbon-based copper azide composite energetic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a core-shell structure carbon-based copper azide composite energetic material and a preparation method thereof. The composite energetic material takes large-particle copper azide as a core, takes amorphous carbon with uniformly distributed copper azide as a shell, constructs a Cu@MOF hybrid body with a core-shell structure by precisely controlling the dissolution rate and the MOF crystallization rate of cuprous oxide, obtains an amorphous carbon composite material embedded with cuprous oxide nano particles by calcining on the basis, and constructs the carbon-based copper azide composite energetic material with the core-shell structure by gas-solid phase azide reaction. The composite energetic material disclosed by the invention utilizes the topological structure of the three-dimensional metal organic framework material to uniformly isolate the copper azide component in the energetic system, so that on one hand, the advantage of high energy density of copper azide is exerted, and on the other hand, the sensitivity of the copper azide is greatly reduced by utilizing the carbon material, and the prepared composite energetic material has the excellent performance of high energy insensitive.
Description
Technical Field
The invention belongs to the technical field of energetic materials, and relates to a core-shell structure carbon-based copper azide composite energetic material and a preparation method thereof.
Background
There is an increasing research on copper azide, and how to reduce the electrostatic sensitivity of copper azide is a serious issue. The approach to reduce the electrostatic sensitivity of copper azide is to compound a material with strong conductivity (such as CNTs, carbonized MOF materials, etc.) to reduce the electrostatic sensitivity, prevent the explosion caused by electrostatic induction, and not reduce the detonation capability.
The use of metal-organic framework compounds in energetic materials falls into two categories, respectively: constructing E-MOF by coordination of an energy-containing organic functional ligand and metal center ion; the composite E-MOF is prepared by taking non-energetic MOFs as a carrier.
The energy-containing organic functional ligands in the first class include: three main classes of energetic small molecule ligands, nitrogen-rich heterocyclic ligands and high-energy multi-explosive ligands. The energetic small molecule ligand comprises azide anions, hydrazine and derivatives thereof, and the high nitrogen content of the ligand ensures that the complex has higher heat of detonation. Five-membered nitrogen-rich heterocycle and its derivative are the nitrogen-rich ligand which is studied more in constructing E-MOF material. High-energy groups such as nitro, gem-dinitro, nitro amine and the like are introduced into the energetic ligand, so that the energy level of the E-MOF can be effectively improved.
The second class of work has few reports at home and abroad, mainly uses non-energetic copper-based MOF (such as HKUST-1) as a precursor to prepare a copper azide composite energetic material, and in 2016, literature (Wang Q, feng X, wang S, et al, metal-organic framework templated synthesis of copper azide as the primary explosive with low electrostatic sensitivity and excellent initiation ability [ J ]. Advanced Materials, 2016, 28 (28): 5766-5766.) reports that the MOF is carbonized at high temperature and then reacts with hydrogen azide gas in situ to prepare the copper azide, so that the electrostatic insensitive porous carbon composite energetic material with the carbon skeleton uniformly coating the copper azide is obtained. The work utilizes the pore channel structural characteristics of MOF, selects HKUST-1 containing copper ions as a substrate, removes oxygen and hydrogen in the HKUST-1 in a carbonization mode, exposes active sites of the copper ions, and maintains other atomic ordering and pore channel structural characteristics in the original structure. This porous nature allows the compound to be more thorough in performing the gas-solid azide reaction. After ordered atoms in the HKUST-1 structure are ordered and carbonized, copper azide molecules generated by the azide reaction can be effectively isolated. Meanwhile, the literature reports (Wang Q, han J, zhang Y, et al Fabrication of Copper Azide Film through Metal-Organic Framework for Micro-Initiator Applications [ J ]. ACS Applied Materials & Interfaces, 2019, 11:8081-8088) that this copper azide film was further assembled in a micro-initiation device that successfully detonated a secondary explosive CL-20. The obtained composite material has the characteristics of high energy and low sensitivity, and effectively overcomes the defects of sensitivity and unsafe of the traditional initiating explosive. However, since the composite energetic material prepared by the method takes the copper-containing MOF material as a precursor, the content of copper azide depends on the content of copper ions in the MOF, the content of copper ions in the MOF is fixed, and the content is less, so the composite energetic material has lower energy density.
Disclosure of Invention
The invention aims to provide a safe and environment-friendly high-energy-insensitivity core-shell structure carbon-based copper azide composite energetic material and a preparation method thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions: the composite material takes large-particle copper azide as a core and takes amorphous carbon with uniformly distributed copper azide as a shell.
The preparation method of the core-shell structure carbon-based copper azide composite energetic material comprises the following steps:
step 1, heating a benzyl alcohol solution of nano cuprous oxide to 80+/-10 ℃, and adding trimesic acid (H 3 Adding the ethanol solution of BTC) into the benzyl alcohol solution of nano cuprous oxide, stirring for 2.0-3.0 h, and centrifugally drying the product to obtain Cu 2 O@MOF hybrid material;
step 2, calcining the product obtained in the step 1 at 400-450 ℃ for 2-3 hours in argon atmosphere, and naturally cooling to room temperature to obtain an amorphous carbon precursor sample embedded with cuprous oxide nano particles;
step 3, at HN 3 And (3) carrying out gas-solid phase azide reaction on the sample obtained in the step (2) for 48-72 h in the atmosphere to obtain the composite material.
Preferably, in the step 1, the nano cuprous oxide is obtained by respectively dissolving copper acetate, glucose and polyvinylpyrrolidone in diethylene glycol, mixing the obtained three solutions, heating to 100+/-20 ℃, stirring and reacting for 1-3 hours, washing and centrifuging.
Preferably, in step 1, cuprous oxide is mixed with H 3 The molar ratio of BTC is 0.7-0.8.
Preferably, in step 2, the rate of temperature increase is 10deg.C/min.
Preferably, in step 3, HN 3 Atmosphere by dilutingDrop nitric acid into NaN 3 The method comprises the steps of generating in a solution, wherein the mass concentration of dilute nitric acid is 3-5%; naN (NaN) 3 The mass concentration of the solution is 3-5%.
Preferably, in step 3, the temperature of the azide reaction is from room temperature to 50 ℃.
Preferably, in the step 3, the azide reaction time is 60-72 h.
Compared with the prior art, the invention has the remarkable advantages that:
(1) By encapsulating cuprous oxide nanoparticles in copper-containing MOFs, the dissolution rate of the metal oxide and the crystallization rate of the MOFs are precisely matched, and Cu with a core-shell structure is constructed 2 O@MOF hybrid to obtain the porous composite material with the metal-organic framework with open mesopores and high specific surface area uniformly coated with cuprous oxide nano particles. And calcining to obtain the amorphous carbon composite precursor embedded with the cuprous oxide nano particles. The preparation method is simple, and the obtained structure is excellent.
(2) The porous carbon composite energetic material of amorphous carbon uniformly coated with copper azide is obtained by directly introducing the azide gas into an open pore canal of the material and constructing a copper azide energetic system in situ, and the copper azide component in the energetic system is uniformly isolated by utilizing the topological structure of the three-dimensional organic metal framework material, so that the sensitivity of the material is greatly reduced. Meanwhile, the cuprous oxide core becomes high-energy copper azide after being azide. The obtained energetic material has excellent performance of high energy insensitive.
Drawings
FIG. 1 shows Cu 2 Schematic structural diagram of a device for calcining and carbonizing O@MOF hybrid.
FIG. 2 is a schematic diagram of an apparatus for the azide reaction.
FIG. 3 is a Cu film obtained in step 1 of example 1 2 SEM image of O @ MOF hybrids.
Fig. 4 is an SEM image of the amorphous carbon precursor of the embedded cuprous oxide nanoparticles prepared in step 2 of example 1.
Fig. 5 is an SEM image of the core-shell structure carbon-based copper azide composite energetic material prepared in step 3 of example 1.
FIG. 6 is a schematic diagram of the structure of the core-shell structure carbon-based copper azide composite energetic material prepared in step 3 of example 1.
Detailed Description
The invention will be described in further detail with reference to the accompanying drawings and specific examples.
Example 1
Preparation of core-shell structure carbon-based copper azide composite energetic material:
step 1, copper acetate (15 mmol), glucose (100 mmol) and polyvinylpyrrolidone (22.5 mmol) were dissolved in 50mL of diethylene glycol, respectively. And (3) heating the three solutions to 100 ℃ in an oil bath after mixing, magnetically stirring for 2 hours, and washing and centrifuging the obtained product to obtain the cuprous oxide nano particles. Cuprous oxide nanoparticles (2.5 mmol) were dissolved in 200mL of benzyl alcohol to obtain benzyl alcohol solution of cuprous oxide nanoparticles; will H 3 BTC (3.35 mmol) was dissolved in ethanol to give H 3 An ethanol solution of BTC. Heating cuprous oxide nanoparticle benzyl alcohol solution in water bath at 80deg.C, and collecting H 3 The ethanol solution of BTC is poured into benzyl alcohol solution of cuprous oxide nano particles and magnetically stirred for 2.5h. The Cu obtained 2 The O@MOF hybrid was dried by centrifugation.
Step 2, the Cu is processed 2 The O@MOF hybrid is placed in the middle of a corundum tube of a vacuum tube furnace shown in fig. 1, argon is introduced while heating, a vacuum pump is opened for vacuum pumping, the vacuum degree is controlled to be maintained at-0.05 Mpa, the temperature in the tube furnace is raised to 450 ℃ at the heating rate of 10 ℃/min, the temperature is kept for two hours, and the amorphous carbon precursor sample with cuprous oxide nano particles distributed is obtained after natural cooling to room temperature.
Step 3, weighing 2g of NaN 3 Dissolving in 50ml water to prepare NaN 3 A solution. Placing the above sample on a sample stage shown in FIG. 2, sealing the container, introducing nitrogen for 10min, weighing 2g of concentrated nitric acid, dissolving in 50ml of water, and dripping into NaN 3 In the solution, the mixture was heated to 40℃in a water bath and subjected to an azide reaction for 72 hours. After the experiment is finished, introducing nitrogen to discharge HN 3 The gas, which is tested, is tested to obtain the composite energetic material, wherein the electrostatic sensitivity is 1.51mJ, and the exothermic peak temperature is 210.9 ℃.
FIG. 1 shows Cu 2 Schematic structural diagram of a device for calcining and carbonizing O@MOF hybrid. 1 is a flowmeter, 2 is a vacuum tube furnace, 3 is a sample, and 4 is a vacuum pump.
FIG. 2 is a schematic diagram of an apparatus for the azide reaction. 5 is NaN 3 Reagent solution, 6 is a constant temperature water bath kettle, 7 is a sample table, 8 is a magnetic stirrer, 9 is a device for absorbing discharged HN 3 NaOH solution of gas.
FIG. 3 shows Cu obtained in example 1 2 SEM image of O @ MOF hybrids. As is apparent from FIG. 3, cu 2 O as a core is surrounded by MOF material, the diameter of the core being about 100nm.
Fig. 4 is an SEM image of an amorphous carbon precursor of the embedded cuprous oxide nanoparticles prepared in example 1. As is apparent from FIG. 4, cu 2 O substantially maintains the original morphology after calcination and carbonization, MOF is calcined to amorphous carbon, cu 2 O as a core is encapsulated in amorphous carbon obtained by carbonization of MOF.
Fig. 5 is an SEM image of the core-shell carbon-based copper azide composite energetic material prepared in example 1. It is apparent from FIG. 5 that Cu is distributed in amorphous carbon 2 O is subjected to azidation to obtain copper azide with morphology relative to Cu 2 The O precursor is more dispersed due to the transition of morphology of the cuprous oxide nanoparticles after the gas-solid phase azide reaction. It can be seen from fig. 5 that the copper azide is still uniformly coated with amorphous carbon.
FIG. 6 is a schematic diagram of the structure of the core-shell carbon-based copper azide composite energetic material prepared in example 1.
Example 2
Preparation of core-shell structure carbon-based copper azide composite energetic material:
step 1, copper acetate (15 mmol), glucose (100 mmol) and polyvinylpyrrolidone (22.5 mmol) were dissolved in 50mL of diethylene glycol, respectively. The three solutions were heated to 100deg.C in a mixed oil bath and magnetically stirred for 2h. The resulting product was washed and centrifuged. Obtaining cuprous oxide nano particles; cuprous oxide (3 mmol) was dissolved in 200mL benzyl alcohol; will H 3 BTC (4 mmol) was dissolved in ethanol. Heating cuprous oxide benzyl alcohol solution in water bath at 80deg.C, and heatingH 3 The ethanol solution of BTC was poured into benzyl alcohol solution of cuprous oxide and magnetically stirred for 2.5h. Centrifugal drying of the product;
and 2, placing the sample in the middle of a corundum tube of a vacuum tube furnace, heating, introducing argon, opening a vacuum pump for vacuum pumping, controlling the vacuum degree to be maintained at-0.05 Mpa, heating the temperature in the tube furnace to 450 ℃ at a heating rate of 10 ℃/min, maintaining for two hours, and naturally cooling to room temperature to obtain the sample.
Step 3, weighing 2g of NaN 3 The solution was prepared by dissolving in 50ml of water. Placing the sample on a sample stage in a container, sealing the container, introducing nitrogen for 10min, weighing 2g of concentrated nitric acid, dissolving in 50ml of water, and dripping to NaN 3 The solution was heated to 40℃by water bath and the experiment was run for 48h. After the experiment is finished, introducing nitrogen to discharge HN 3 The gas, which is tested, obtained the composite energetic material of the invention, has an electrostatic sensitivity of 1.49mJ and an exothermic peak temperature of 209.6 ℃.
Example 3
Preparation of core-shell structure carbon-based copper azide composite energetic material:
step 1, copper acetate (15 mmol), glucose (100 mmol) and polyvinylpyrrolidone (22.5 mmol) were dissolved in 50mL of diethylene glycol, respectively. The three solutions were heated to 100deg.C in a mixed oil bath and magnetically stirred for 2h. The resulting product was washed and centrifuged. Obtaining cuprous oxide nano particles; cuprous oxide (2.8 mmol) was dissolved in 200mL benzyl alcohol; will H 3 BTC (3.75 mmol) was dissolved in ethanol. Heating cuprous oxide benzyl alcohol solution in water bath at 80deg.C, and collecting H 3 The ethanol solution of BTC was poured into benzyl alcohol solution of cuprous oxide and magnetically stirred for 2.5h. Centrifugal drying of the product;
and 2, placing the sample in the middle of a corundum tube of a vacuum tube furnace, heating, introducing argon, opening a vacuum pump for vacuum pumping, controlling the vacuum degree to be maintained at-0.05 Mpa, heating the temperature in the tube furnace to 400 ℃ at a heating rate of 10 ℃/min, maintaining for two hours, and naturally cooling to room temperature to obtain the sample.
Step 3, weighing 2g of NaN 3 The solution was prepared by dissolving in 50ml of water. Sample for placing sample in containerOn a bench, the vessel was closed and purged with nitrogen for 10min, 2g of concentrated nitric acid was weighed and dissolved in 50ml of water and added dropwise to NaN 3 The solution was heated to 40℃by water bath and the experiment was run for 60h. After the experiment is finished, introducing nitrogen to discharge HN 3 The gas, which is tested, is tested to obtain the composite energetic material, wherein the electrostatic sensitivity is 1.47mJ, and the exothermic peak temperature is 206.6 ℃.
Comparative example 1
This comparative example is essentially the same as example 1, with the only difference that the azide reaction time is 24 hours, and the result shows that the reaction is incomplete due to the too short time, and that elemental copper and cuprous azide crystals that are not completely azide are present in the product.
Comparative example 2
This comparative example is essentially the same as example 1, except that the temperature in the tube furnace is 300 ℃, which indicates that it cannot be used as a precursor material for the azide reaction because the temperature is too low to fully carbonize the MOF material.
Claims (7)
1. The carbon-based copper azide composite energetic material with the core-shell structure is characterized in that the composite energetic material takes large-particle copper azide as a core and takes amorphous carbon with copper azide uniformly distributed as a shell;
the preparation method comprises the following steps:
step 1, heating a benzyl alcohol solution of nano cuprous oxide to 80+/-10 ℃, and heating H 3 Adding the BTC ethanol solution into the nano cuprous oxide benzyl alcohol solution, stirring for 2.0-3.0 h, and centrifugally drying the product to obtain Cu 2 O@MOF hybrid material;
step 2, calcining the product obtained in the step 1 at 400-450 ℃ for 2-3 hours in an argon atmosphere, and naturally cooling to room temperature to obtain an amorphous carbon precursor sample embedded with cuprous oxide nano particles;
step 3, at HN 3 Carrying out an azide reaction on the sample obtained in the step 2 at the temperature of between room temperature and 50 ℃ for 60-72 h under the atmosphere to obtain the composite material;
in the step 1, cuprous oxide and H 3 The molar ratio of BTC is 0.7-0.8;
in the step 2, the heating rate is 10 ℃/min;
in step 3, HN 3 Atmosphere by dropping dilute nitric acid into NaN 3 The method comprises the steps of generating in a solution, wherein the mass concentration of dilute nitric acid is 3-5%; naN (NaN) 3 The mass concentration of the solution is 3-5%;
the nano cuprous oxide is prepared by respectively dissolving copper acetate, glucose and polyvinylpyrrolidone in diethylene glycol, mixing the obtained three solutions, heating to 100+/-20 ℃, stirring for reacting for 1-3 h, washing and centrifuging.
2. The method of preparing a composite energetic material according to claim 1, comprising the steps of:
step 1, heating a benzyl alcohol solution of nano cuprous oxide to 80+/-10 ℃, and heating H 3 Adding the BTC ethanol solution into the nano cuprous oxide benzyl alcohol solution, stirring for 2.0-3.0 h, and centrifugally drying the product to obtain Cu 2 O@MOF hybrid material;
step 2, calcining the product obtained in the step 1 at 400-450 ℃ for 2-3 hours in an argon atmosphere, and naturally cooling to room temperature to obtain an amorphous carbon precursor sample embedded with cuprous oxide nano particles;
step 3, at HN 3 And (3) carrying out an azide reaction on the sample obtained in the step (2) for 60-72 h in the atmosphere to obtain the composite material.
3. The method of claim 2, wherein in the step 1, the nano cuprous oxide is obtained by respectively dissolving copper acetate, glucose and polyvinylpyrrolidone in diethylene glycol, mixing the obtained three solutions, heating to 100+/-20 ℃, stirring and reacting for 1-3 h, washing and centrifuging.
4. The method of claim 2, wherein in step 1, cuprous oxide is mixed with H 3 The molar ratio of BTC is 0.7-0.8.
5. The method of claim 2, wherein in step 2, the rate of temperature increase is 10 ℃/min.
6. The method of claim 2, wherein in step 3, HN 3 Atmosphere by dropping dilute nitric acid into NaN 3 The method comprises the steps of generating in a solution, wherein the mass concentration of dilute nitric acid is 3-5%; naN (NaN) 3 The mass concentration of the solution is 3-5%.
7. The method of claim 2, wherein in step 3, the azide reaction temperature is from room temperature to 50 ℃.
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