Nano composite material and preparation method and application thereof
阅读说明：本技术 一种纳米复合材料及其制备方法和应用 (Nano composite material and preparation method and application thereof ) 是由 李国平 李胜楠 罗运军 王晓青 于 2021-09-15 设计创作，主要内容包括：本发明提供了一种PN/Cu/CoCuP-(2)O-(7)纳米复合材料及其制备方法和应用,属于纳米材料技术领域。首先将黑磷烯(PN)、醇溶剂和丙三醇混合；然后加入铜盐和钴盐,将分散液转移至高压釜中加热,随后洗涤得到初步产物；最后在保护气氛下煅烧即得产物。本发明采用溶剂热法,该方法相对简单而且易于控制,且密闭体系可以有效防止有毒物质的挥发。该纳米复合材料不但物相的形成、粒径的大小、形态可以控制,而且黑磷烯具有大的比表面积,良好的导电性和导热性,PN的存在不仅可以抑制Cu、CoCuP-(2)O-(7)粒子团聚而且同时还可以提高其热导率。该纳米复合材料新产品可在催化剂、电化学等方面广泛应用。(The invention provides a PN/Cu/CoCuP 2 O 7 A nano composite material and a preparation method and application thereof belong to the technical field of nano materials. Firstly, mixing the black phosphorus alkene (PN), an alcohol solvent and glycerol; then adding copper salt and cobalt salt, transferring the dispersion liquid into a high-pressure kettle for heating, and then washing to obtain a primary product; and finally calcining the mixture under a protective atmosphere to obtain a product. The invention adopts a solvothermal method, the method is relatively simple and easy to control, and a closed system can effectively prevent the volatilization of toxic substances. The nano composite material not only can form phase, and the size and the form of the grain diameter can beThe black phosphorus alkene has large specific surface area, good electrical conductivity and thermal conductivity, and the existence of PN can inhibit Cu and CoCuP 2 O 7 The particles agglomerate and at the same time the thermal conductivity can be increased. The new product of the nano composite material can be widely applied to the aspects of catalysts, electrochemistry and the like.)
1. PN/Cu/CoCuP2O7The preparation method of the nano composite material is characterized by comprising the following steps:
mixing the black phosphorus alkene dispersion liquid, copper salt and cobalt salt, and then heating for reaction to obtain a reaction product;
and calcining the reaction product in a protective atmosphere to obtain the nano composite material.
2. The method of preparing the nanocomposite as claimed in claim 1, wherein the method of preparing the black limonene dispersion comprises the steps of:
the black phosphorus crystal is refined into powder to prepare black phosphorus dispersion liquid;
carrying out ultrasonic treatment, centrifugation and freeze drying treatment on the black phosphorus dispersion liquid to obtain black phosphorus alkene;
mixing the black phosphorus alkene, the alcohol solvent and the glycerol to obtain the black phosphorus alkene dispersion liquid.
3. The method for preparing the nanocomposite material according to claim 2, wherein the concentration of the black phosphorus dispersion liquid is 1 to 10 mg/ml; the power of the ultrasonic wave is 45-95%;
the centrifugal rotating speed is 5000-10000 rpm, the freeze drying temperature is-50 ℃ to-10 ℃, and the freeze drying time is 3-10 h.
4. The preparation method of the nanocomposite material as claimed in claim 3, wherein the mass volume ratio of the black phosphene to the alcohol solvent to the glycerol is 70-90 mg: 30-50 ml: 5-10 ml.
5. The method for preparing a nanocomposite material as claimed in claim 4, wherein the alcohol solvent comprises one or more of isopropanol, methanol, ethanol, ethylene glycol and polyethylene glycol.
6. The method for preparing the nanocomposite material as claimed in claim 5, wherein the concentration of the black phosphorus alkene dispersion liquid is 1.0-2.8 mg/ml;
the volume mol ratio of the black phosphorus alkene dispersion liquid to the copper salt to the cobalt salt is 100-160 ml: 1.0-1.5 mmol: 3.0 to 3.5 mmol.
7. The method of claim 6, wherein the copper salt comprises Cu (NO)3)2Hydrate of (2), Cu (CH)3COO)2Hydrate and CuCl of2One or more of the hydrates of (a); the cobalt salt comprises Co (NO)3)2Hydrate of (1), Co (CH)3COO)2Hydrate and CoCl of2One or more of the hydrates of (a).
8. The method for preparing the nanocomposite material according to claim 7, wherein the temperature of the heating reaction is 100 to 200 ℃, and the time of the heating reaction is 2 to 10 hours;
the calcining temperature is 200-600 ℃, and the calcining time is 60-400 min;
the protective atmosphere is nitrogen or argon.
9. PN/Cu/CoCuP obtained by the preparation method of any one of claims 1 to 82O7A nanocomposite material.
10. Use of a nanocomposite as claimed in claim 9 for improving the thermal performance of an energy-containing material, wherein the energy-containing material comprises ammonium perchlorate, explosive hexogen and hexanitrohexaazaisowurtzitane.
Technical Field
The invention relates to the technical field of nano materials, in particular to a nano composite material and a preparation method and application thereof.
Background
The solid propellant is an energetic composite material which is formed by mixing an adhesive serving as a matrix with energetic solid particles (an oxidant, a metal fuel and the like), is a power source of engines such as rockets, missiles, space vehicles and the like, and converts chemical energy into heat energy through combustion, wherein the oxidant accounts for 60-90% of the total amount of the propellant, the thermal decomposition temperature and the heat release quantity of the oxidant directly influence the combustion performance of the propellant, the combustion performance is a main index for evaluating the performance of the propellant, and the energy release rate, the efficiency and the stability of the propellant are determined. However, the prior oxidant has higher decomposition temperature and lower heat release, is not beneficial to the combustion of the propellant, improves the thermal decomposition performance and has important significance for improving the combustion performance of the propellant. The introduction of the catalyst can effectively lower the pyrolysis temperature of the oxidant, and a lower pyrolysis temperature and a higher exotherm can result in a higher combustion rate.
To date, a number of catalysts have been developed and used in solid propellants. A great deal of research shows that the transition metal nanoparticles (Ni, Cu, Al, etc.) and the metal oxide nanoparticles (Fe)2O3、CuO、TiO2、Mn3O4) The nanometer catalyst can improve the catalytic performance of thermal decomposition of the oxidant, but the pure nanometer particles are small in size, high in surface activity and easy to agglomerate, cannot be in full contact with a medium to reduce the catalytic activity, are not beneficial to combustion of the propellant, and lose a plurality of excellent performances of the nanometer material.
The nano composite material is prepared by compounding the graphene and the metal nano particles or the metal oxide nano particles, and the graphene with an ultra-large specific surface area can inhibit particle agglomeration. In 2014, a novel two-dimensional material single-layer black phosphorus-black phosphorus alkene (PN) is prepared by an adhesive tape technology, and compared with graphene, the maximum theoretical surface area of the black phosphorus alkene is 2400m2·g-1Has higher conductivity (the carrier mobility reaches 160000 cm)2/(V·s) and thermal conductivity (thermal conductivity 8500W/(m.K)), and black phosphorus alkene can be mixed with O2The reaction releases a large amount of heat to catalyze the decomposition of the oxidant, which is a property that graphene does not have. The composite material not only has the quantum size effect, small size effect, surface and interface effect, macroscopic quantum tunnel effect and the like of single nano particles, but also has synergistic effect, fully exerts various excellent characteristics of the single nano particles, ensures that the nano energetic material has practical significance, meets the requirements of different occasions, and simultaneously provides an effective method for manufacturing novel composite energetic materials.
At present, the preparation methods of the nano composite material mainly comprise a solvothermal method, a sol-gel method, a spray evaporation method, a supercritical fluid recrystallization method, an electrostatic spray recrystallization method, a mechanical grinding method, a solvent-non-solvent recrystallization method, a freeze drying method, a precipitation method, a microemulsion method and the like.
However, the yield of the nano composite material obtained in the prior art is low, and the effect in practical application is not good, so that the technical problem that the nano composite material which is simple in process, high in product yield and capable of remarkably improving the performance of the catalyst is needed to be solved urgently is obtained.
Disclosure of Invention
The invention aims to provide a nano composite material and a preparation method and application thereof, which solve the problems of high decomposition temperature, slow decomposition process, difficult thorough combustion and low heat release of the conventional oxidant, and solve the problems of phase formation, uncontrollable particle size and morphology and easy agglomeration of the nano composite material prepared by a solvothermal method.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a PN/Cu/CoCuP2O7The preparation method of the nano composite material comprises the following steps:
mixing the black phosphorus alkene dispersion liquid, copper salt and cobalt salt, and then heating for reaction to obtain a reaction product;
and calcining the reaction product in a protective atmosphere to obtain the nano composite material.
Further, the preparation method of the black phosphorus alkene dispersion liquid comprises the following steps:
the black phosphorus crystal is refined into powder to prepare black phosphorus dispersion liquid;
carrying out ultrasonic treatment, centrifugation and freeze drying treatment on the black phosphorus dispersion liquid to obtain black phosphorus alkene;
mixing the black phosphorus alkene, the alcohol solvent and the glycerol to obtain the black phosphorus alkene dispersion liquid.
Further, the concentration of the black phosphorus dispersion liquid is 1-10 mg/ml;
the power of the ultrasonic wave is 45-95%;
the centrifugal rotating speed is 5000-10000 rpm, the freeze drying temperature is-50 ℃ to-10 ℃, and the freeze drying time is 3-10 h.
Further, the mass volume ratio of the black phosphorus alkene to the alcohol solvent to the glycerol is 70-90 mg: 30-50 ml: 5-10 ml.
Further, the alcohol solvent comprises one or more of isopropanol, methanol, ethanol, ethylene glycol and polyethylene glycol.
Further, the concentration of the black phosphorus alkene dispersion liquid is 1.0-2.8 mg/ml;
the volume mol ratio of the black phosphorus alkene dispersion liquid to the copper salt to the cobalt salt is 100-160 ml: 1.0-1.5 mmol: 3.0 to 3.5 mmol.
Further, the copper salt comprises Cu (NO)3)2Hydrate of (2), Cu (CH)3COO)2Hydrate and CuCl of2One or more of the hydrates of (a); the cobalt salt comprises Co (NO)3)2Hydrate of (1), Co (CH)3COO)2Hydrate and CoCl of2One or more of the hydrates of (a).
Further, the heating reaction temperature is 100-200 ℃, and the heating reaction time is 2-10 hours;
the calcining temperature is 200-600 ℃, and the calcining time is 60-400 min;
the protective atmosphere is nitrogen or argon.
The invention provides a PN/Cu/CoCuP2O7A nanocomposite material.
The invention provides a PN/Cu/CoCuP2O7Use of a nanocomposite for improving the thermal properties of an energetic material.
Further, the energetic material comprises ammonium perchlorate, explosive hexogen and hexanitrohexaazaisowurtzitane.
The invention has the beneficial effects that:
1. the preparation method of the nano composite material has the advantages of phase formation, controllable particle size and form and many chemical reaction active sites.
2. The black phosphorus alkene prepared by the invention has large specific surface area and good electrical conductivity and thermal conductivity, and the existence of PN can inhibit Cu and CoCuP2O7The particle agglomeration can also improve the thermal conductivity of the composite material.
3. The method has the advantages of simple and common treatment, drying and calcining equipment, no need of expensive equipment, low experimental cost and green and environment-friendly preparation process.
4. The nano composite material prepared by the invention has wide application, can be used for special requirements of biological medicines, electrochemistry, aviation materials and the like, can reduce the pyrolysis temperature of ammonium perchlorate, explosive hexogen and hexanitrohexaazaisowurtzitane energetic materials, and can improve the heat release.
Drawings
FIG. 1 is a SEM comparative image of the nanocomposites obtained in comparative example, example 1 and example 2 from top to bottom;
FIG. 2 is the XRD pattern and Cu, CoCuP of the nanocomposite obtained by calcination under argon atmosphere in example 12O7Standard XRD pattern of (a);
FIG. 3 is the XRD pattern and Cu, CoCuP of the nanocomposite obtained by calcination under nitrogen atmosphere in example 22O7Standard XRD pattern of (a);
FIG. 4 is an XPS plot of Cu2p for the nanocomposite obtained from example 2 calcined under a nitrogen atmosphere;
FIG. 5 is an XPS plot of Cu2p for the nanocomposite obtained from example 1 calcined under an argon atmosphere;
FIG. 6 is an XPS plot of Co2p for the nanocomposite obtained from example 1 calcined under an argon atmosphere;
fig. 7 is an XPS plot of Co2p for the nanocomposite obtained from example 2 calcined under a nitrogen atmosphere.
Detailed Description
The invention provides a PN/Cu/CoCuP2O7The preparation method of the nano composite material comprises the following steps:
mixing the black phosphorus alkene dispersion liquid, copper salt and cobalt salt, and then heating for reaction to obtain a reaction product;
and calcining the reaction product in a protective atmosphere to obtain the nano composite material.
In the invention, the preparation method of the black phosphorus alkene dispersion liquid comprises the following steps:
the black phosphorus crystal is refined into powder to prepare black phosphorus dispersion liquid;
carrying out ultrasonic treatment, centrifugation and freeze drying treatment on the black phosphorus dispersion liquid to obtain black phosphorus alkene;
mixing the black phosphorus alkene, the alcohol solvent and the glycerol to obtain the black phosphorus alkene dispersion liquid.
In the present invention, it is preferable to disperse the black phosphorus crystal powder in water to obtain a black phosphorus dispersion liquid; the concentration of the black phosphorus dispersion liquid is 1-10 mg/ml, preferably 2-9 mg/ml, and more preferably 3-8 mg/ml.
In the invention, the power of the ultrasonic wave is 45-95%, preferably 50-90%, further preferably 60-80%, and more preferably 70%; the ultrasonic treatment time is 30-120 min, preferably 50-100 min, and more preferably 60-90 min.
In the invention, the rotation speed of centrifugation is 5000-10000 rpm, the freeze drying temperature is-50 ℃ to-10 ℃, the freeze drying time is 3-10 h, the preferred rotation speed of centrifugation is 6000-8000 rpm, the freeze drying temperature is-40 ℃ to-20 ℃, the freeze drying time is 4-8 h, the further preferred rotation speed of centrifugation is 7000rpm, the freeze drying temperature is-30 ℃, and the freeze drying time is 6 h.
In the invention, the mass-volume ratio of the black phosphorus alkene to the alcohol solvent to the glycerol is 70-90 mg: 30-50 ml: 5-10 ml, preferably 75-85 mg: 35-45 ml: 6-9 ml, more preferably 80 mg: 40 ml: 8 ml.
In the invention, the alcohol solvent comprises one or more of isopropanol, methanol, ethanol, ethylene glycol and polyethylene glycol, preferably one or more of isopropanol, methanol, ethanol and polyethylene glycol, and more preferably isopropanol.
In the invention, the concentration of the black phosphorus alkene dispersion liquid is 1.0-2.8 mg/ml, preferably 1.5-2.5 mg/ml, and more preferably 2.0 mg/ml.
In the invention, the volume mol ratio of the black phosphorus alkene dispersion liquid to the copper salt to the cobalt salt is 100-160 ml: 1.0-1.5 mmol: 3.0-3.5 mmol, preferably 120-140 ml: 1.2-1.4 mmol: 3.1 to 3.4mmol, more preferably 130 ml: 1.3 mmol: 3.2 mmol.
In the present invention, the copper salt comprises Cu (NO)3)2Hydrate of (2), Cu (CH)3COO)2Hydrate and CuCl of2Preferably one or more of the hydrates of (a), preferably Cu (NO)3)2·6H2O。
In the present invention, the cobalt salt comprises Co (NO)3)2Hydrate of (1), Co (CH)3COO)2Hydrate and CoCl of2Preferably Co (NO)3)2·6H2O。
In the invention, the temperature of the heating reaction is 100-200 ℃, preferably 120-180 ℃, and further preferably 150 ℃; the heating reaction time is 2-10 h, preferably 3-9 h, and more preferably 4-8 h.
In the invention, the calcining temperature is 200-600 ℃, preferably 300-500 ℃, and more preferably 400 ℃; the calcination time is 60-400 min, preferably 100-350 min, and more preferably 200-250 min.
In the present invention, the protective atmosphere is nitrogen or argon, preferably argon.
The invention provides a PN/Cu/CoCuP2O7A nanocomposite material.
The invention provides a PN/Cu/CoCuP2O7Use of a nanocomposite for improving the thermal properties of an energetic material.
In the present invention, the energetic material comprises ammonium perchlorate, explosive hexogen, and hexanitrohexaazaisowurtzitane, preferably ammonium perchlorate and hexanitrohexaazaisowurtzitane.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Firstly, blowing and grinding black phosphorus crystals in a mortar by using argon gas until the black phosphorus crystals are powder with metal luster, transferring the black phosphorus powder into a beaker filled with the argon gas, adding a proper amount of water into the beaker, and preparing a black phosphorus dispersion liquid with the concentration of 1 mg/ml. Placing the beaker in an ice bath, placing the beaker into a cell crusher, under the argon atmosphere, enabling the bottom of a sample to be about 2cm away from an ultrasonic probe, enabling the ultrasonic power to be 45%, working for 8 hours in a mode of ultrasonic on for 2s and ultrasonic off for 4s, centrifuging for 10 minutes at the rotating speed of 7000r/min, and then freeze-drying for 3 hours at the temperature of 50 ℃ below zero to obtain the black phosphorus alkene;
secondly, ultrasonically dispersing 80mg of the black phosphorus alkene obtained in the first step into 40ml of isopropanol, wherein the ultrasonic power is 95%, and the ultrasonic time is 30 minutes; then adding 8ml of glycerol into the isopropanol dispersion liquid of the black phosphorus alkene, mechanically stirring at 250rpm/min for 1 hour to prepare the black phosphorus alkene dispersion liquid, wherein the whole process needs the protection of argon atmosphere;
thirdly, adding the total amount (4.5mmol) of Cu (NO) into the black phosphorus alkene dispersion liquid obtained in the second step3)2·6H2O and Co (NO)3)2·6H2O (molar ratio 1:2), mechanically stirring at 250rpm/min for 0.2 hr, transferring into 100mL autoclave, heating at 180 deg.C for 6 hr, cooling to room temperature, washing with deionized water for several times, and standingFreezing at-80 deg.C for 3 hr to obtain nanometer composite material;
fourthly, placing the nano composite material obtained in the third step into a quartz tube of a tube furnace, firstly pumping the nano composite material into a vacuum state by using a vacuum pump, then introducing argon to further exhaust air, repeating the process for 3 times, then heating to 500 ℃ at the speed of 5 ℃/min, and calcining at high temperature for 300min to obtain PN/Cu/CoCuP2O7The nanocomposite had a product yield of 94%.
Example 2
Firstly, the black phosphorus crystal is blown and ground in a mortar by argon gas until the black phosphorus crystal has metallic luster, the black phosphorus powder is transferred into a beaker filled with nitrogen gas, and a proper amount of water is added into the beaker to prepare a black phosphorus dispersion liquid with the concentration of 1 mg/ml. Placing the beaker in an ice bath, placing the beaker into a cell disruptor, under the nitrogen atmosphere, enabling the bottom of a sample to be about 2cm away from an ultrasonic probe, enabling the ultrasonic power to be 50%, working for 8 hours in a mode of ultrasonic on for 2s and ultrasonic off for 4s, centrifuging for 10 minutes at a rotating speed of 6000r/min, and then freeze-drying for 4 hours at the temperature of minus 30 ℃ to obtain the black phosphorus alkene;
secondly, ultrasonically dispersing 70mg of the black phosphorus alkene obtained in the first step in 40ml of methanol, wherein the ultrasonic power is 90%, and the ultrasonic time is 30 minutes; then adding 8ml of glycerol into the isopropanol dispersion liquid of the black phosphorus alkene, mechanically stirring at 250rpm/min for 1 hour to prepare the black phosphorus alkene dispersion liquid, wherein the whole process needs protection of nitrogen atmosphere;
thirdly, adding the total amount (4.5mmol) of Cu (NO) into the black phosphorus alkene dispersion liquid obtained in the second step3)2·6H2O and Co (NO)3)2·6H2O (the molar ratio is 1:3), mechanically stirring at 250rpm/min for 0.2 hour, transferring into a 100mL tetrafluoroethylene autoclave, heating at 180 ℃ for 6 hours, cooling to room temperature after the reaction is finished, washing with deionized water for multiple times, and then freezing at-80 ℃ for 3 hours to obtain the nanocomposite;
fourthly, placing the nano composite material obtained in the third step into a quartz tube of a tube furnace, firstly pumping the nano composite material into a vacuum state by using a vacuum pump, then introducing nitrogen to further exhaust air, repeating the operation for 3 times, then heating the nano composite material to 600 ℃ at the speed of 5 ℃/min, and calcining the nano composite material at a high temperature for 300min to obtain the PN/Cu/based on the moisture content of the PN/CuCoCuP2O7The nanocomposite was produced in 95% yield.
Example 3
Firstly, blowing and grinding black phosphorus crystals in a mortar by using argon gas until the black phosphorus crystals are powder with metal luster, transferring the black phosphorus powder into a beaker filled with the argon gas, adding a proper amount of water into the beaker, and preparing a black phosphorus dispersion liquid with the concentration of 1 mg/ml. Placing the beaker in an ice bath, placing the beaker into a cell crusher, under the argon atmosphere, enabling the bottom of a sample to be about 2cm away from an ultrasonic probe, enabling the ultrasonic power to be 55%, working for 8 hours in a mode of ultrasonic on for 2s and ultrasonic off for 4s, centrifuging for 10 minutes at a rotating speed of 8000r/min, and then freeze-drying for 5 hours at the temperature of minus 20 ℃ to obtain the black phosphorus alkene;
secondly, ultrasonically dispersing 85mg of the black phosphorus alkene obtained in the first step in 40ml of ethanol, wherein the ultrasonic power is 95%, and the ultrasonic time is 30 minutes; then adding 8ml of glycerol into the isopropanol dispersion liquid of the black phosphorus alkene, mechanically stirring at 250rpm/min for 1 hour to prepare the black phosphorus alkene dispersion liquid, wherein the whole process needs the protection of argon atmosphere;
thirdly, adding the total amount (4.5mmol) of Cu (NO) into the black phosphorus alkene dispersion liquid obtained in the second step3)2·6H2O and Co (NO)3)2·6H2O (the molar ratio is 1.0:3.5), mechanically stirring at 250rpm/min for 0.2 hour, transferring into a 100mL autoclave containing tetrafluoroethylene, heating at 160 ℃ for 6 hours, cooling to room temperature after the reaction is finished, washing with deionized water for multiple times, and freezing at-80 ℃ for 3 hours to obtain the nanocomposite;
fourthly, placing the nano composite material obtained in the third step into a quartz tube of a tube furnace, firstly pumping the nano composite material into a vacuum state by using a vacuum pump, then introducing argon to further exhaust air, repeating the process for 3 times, then heating the nano composite material to 450 ℃ at the speed of 5 ℃/min, and calcining the nano composite material at high temperature for 300min to obtain PN/Cu/CoCuP2O7The yield of the product of the nano composite material is 93.5 percent.
Example 4
Firstly, blowing and grinding black phosphorus crystals in a mortar by using argon gas until the black phosphorus crystals are powder with metal luster, transferring the black phosphorus powder into a beaker filled with the argon gas, adding a proper amount of water into the beaker, and preparing a black phosphorus dispersion liquid with the concentration of 1 mg/ml. Placing the beaker in an ice bath, placing the beaker into a cell crusher, under the argon atmosphere, enabling the bottom of a sample to be about 2cm away from an ultrasonic probe, enabling the ultrasonic power to be 60%, working for 8 hours in a mode of ultrasonic on for 2s and ultrasonic off for 4s, centrifuging for 10 minutes at a rotating speed of 10000r/min, and then freeze-drying for 3 hours at-30 ℃ to obtain the black phosphorus alkene;
secondly, ultrasonically dispersing 75mg of the black phosphorus alkene obtained in the first step into 40ml of ethylene glycol, wherein the ultrasonic power is 70%, and the ultrasonic time is 30 minutes; then adding 8ml of glycerol into the isopropanol dispersion liquid of the black phosphorus alkene, mechanically stirring at 250rpm/min for 1 hour to prepare the black phosphorus alkene dispersion liquid, wherein the whole process needs the protection of argon atmosphere;
thirdly, adding the total amount (4.5mmol) of Cu (NO) into the black phosphorus alkene dispersion liquid obtained in the second step3)2·6H2O and Co (NO)3)2·6H2O (the molar ratio is 1.0:2.0), mechanically stirring at 250rpm/min for 0.2 hour, transferring into a 100mL autoclave containing tetrafluoroethylene, heating at 140 ℃ for 6 hours, cooling to room temperature after the reaction is finished, washing with deionized water for multiple times, and freezing at-80 ℃ for 3 hours to obtain the nanocomposite;
fourthly, placing the nano composite material obtained in the third step into a quartz tube of a tube furnace, firstly pumping the nano composite material into a vacuum state by using a vacuum pump, then introducing argon to further exhaust air, repeating the process for 3 times, then heating the nano composite material to 300 ℃ at the speed of 5 ℃/min, and calcining the nano composite material at high temperature for 350min to obtain PN/Cu/CoCuP2O7The nanocomposite was produced in 95% yield.
Example 5
Firstly, the black phosphorus crystal is blown and ground in a mortar by argon gas until the black phosphorus crystal has metallic luster, the black phosphorus powder is transferred into a beaker filled with nitrogen gas, and a proper amount of water is added into the beaker to prepare a black phosphorus dispersion liquid with the concentration of 1 mg/ml. Placing the beaker in an ice bath, placing the beaker into a cell disruptor, under the nitrogen atmosphere, enabling the bottom of a sample to be about 2cm away from an ultrasonic probe, enabling the ultrasonic power to be 65%, working for 8 hours in a mode of ultrasonic on for 2s and ultrasonic off for 4s, centrifuging for 10 minutes at a rotating speed of 6000r/min, and then freeze-drying for 8 hours at the temperature of minus 10 ℃ to obtain the black phosphorus alkene;
secondly, ultrasonically dispersing 80mg of the black phosphorus alkene obtained in the first step into 40ml of polyethylene glycol, wherein the ultrasonic power is 95%, and the ultrasonic time is 30 minutes; then adding 8ml of glycerol into the isopropanol dispersion liquid of the black phosphorus alkene, mechanically stirring at 250rpm/min for 1 hour to prepare the black phosphorus alkene dispersion liquid, wherein the whole process needs the protection of nitrogen atmosphere;
thirdly, adding the total amount (4.5mmol) of Cu (NO) into the black phosphorus alkene dispersion liquid obtained in the second step3)2·6H2O and Co (NO)3)2·6H2O (the molar ratio is 1.2:2.5), mechanically stirring at 250rpm/min for 0.2 hour, transferring into a 100mL autoclave containing tetrafluoroethylene, heating at 130 ℃ for 10 hours, cooling to room temperature after the reaction is finished, washing with deionized water for multiple times, and freezing at-80 ℃ for 3 hours to obtain the nanocomposite;
fourthly, placing the nano composite material obtained in the third step into a quartz tube of a tube furnace, firstly pumping the nano composite material into a vacuum state by using a vacuum pump, then introducing nitrogen to further exhaust air, repeating the process for 3 times, then heating the nano composite material to 600 ℃ at the speed of 5 ℃/min, and calcining the nano composite material at high temperature for 200min to obtain PN/Cu/CoCuP2O7The nanocomposite was produced in 95% yield.
Example 6
Firstly, blowing and grinding black phosphorus crystals in a mortar by using argon gas until the black phosphorus crystals are powder with metal luster, transferring the black phosphorus powder into a beaker filled with the argon gas, adding a proper amount of water into the beaker, and preparing a black phosphorus dispersion liquid with the concentration of 1 mg/ml. Placing the beaker in an ice bath, placing the beaker into a cell crusher, under the argon atmosphere, enabling the bottom of a sample to be about 2cm away from an ultrasonic probe, enabling the ultrasonic power to be 70%, working for 8 hours in a mode of ultrasonic on for 2s and ultrasonic off for 4s, centrifuging for 10 minutes at a rotating speed of 8000r/min, and then freeze-drying for 3 hours at the temperature of minus 20 ℃ to obtain the black phosphorus alkene;
secondly, ultrasonically dispersing 88mg of the black phosphorus alkene obtained in the first step in 40ml of ethylene glycol, wherein the ultrasonic power is 80%, and the ultrasonic time is 30 minutes; then adding 8ml of glycerol into the isopropanol dispersion liquid of the black phosphorus alkene, mechanically stirring at 250rpm/min for 1 hour to prepare the black phosphorus alkene dispersion liquid, wherein the whole process needs the protection of argon atmosphere;
thirdly, obtaining the product in the step twoTo the black phosphorus alkene dispersion of (1), Cu (NO) was added in a total amount (4.5mmol)3)2·6H2O and Co (NO)3)2·6H2O (the molar ratio is 1.5:2), mechanically stirring at 250rpm/min for 0.2 hour, transferring to a 100mL autoclave containing tetrafluoroethylene, heating at 160 ℃ for 6 hours, cooling to room temperature after the reaction is finished, washing with deionized water for multiple times, and freezing at-80 ℃ for 3 hours to obtain the nanocomposite;
fourthly, placing the nano composite material obtained in the third step into a quartz tube of a tube furnace, firstly pumping the nano composite material into a vacuum state by using a vacuum pump, then introducing argon to further exhaust air, repeating the process for 3 times, then heating to 330 ℃ at the speed of 5 ℃/min, and calcining at high temperature for 350min to obtain PN/Cu/CoCuP2O7The product yield of the nanocomposite material is 96.8%.
Example 7
Firstly, the black phosphorus crystal is blown and ground in a mortar by argon gas until the black phosphorus crystal has metallic luster, the black phosphorus powder is transferred into a beaker filled with nitrogen gas, and a proper amount of water is added into the beaker to prepare a black phosphorus dispersion liquid with the concentration of 1 mg/ml. Placing the beaker in an ice bath, placing the beaker into a cell disruptor, under the nitrogen atmosphere, enabling the bottom of a sample to be about 2cm away from an ultrasonic probe, enabling the ultrasonic power to be 75%, working for 8 hours in a mode of ultrasonic on for 2s and ultrasonic off for 4s, centrifuging for 10 minutes at a rotating speed of 6000r/min, and then freeze-drying for 3 hours at the temperature of minus 40 ℃ to obtain the black phosphorus alkene;
secondly, ultrasonically dispersing 90mg of the black phosphorus alkene obtained in the first step into 40ml of isopropanol, wherein the ultrasonic power is 95%, and the ultrasonic time is 30 minutes; then adding 8ml of glycerol into the isopropanol dispersion liquid of the black phosphorus alkene, mechanically stirring at 250rpm/min for 1 hour to prepare the black phosphorus alkene dispersion liquid, wherein the whole process needs the protection of nitrogen atmosphere;
thirdly, adding the total amount (4.5mmol) of Cu (NO) into the black phosphorus alkene dispersion liquid obtained in the second step3)2·6H2O and Co (NO)3)2·6H2O (molar ratio 1:2), mechanically stirring at 250rpm/min for 0.2 hr, transferring into 100mL autoclave, heating at 160 deg.C for 6 hr, cooling to room temperature, washing with deionized water for several times, and cooling to obtain the final productFreezing at-80 deg.C for 3 hr to obtain nanometer composite material;
fourthly, placing the nano composite material obtained in the third step into a quartz tube of a tube furnace, firstly pumping the nano composite material into a vacuum state by using a vacuum pump, then introducing nitrogen to further exhaust air, repeating the process for 3 times, then heating the nano composite material to 450 ℃ at the speed of 5 ℃/min, and calcining the nano composite material at high temperature for 300min to obtain PN/Cu/CoCuP2O7The nanocomposite was produced in 95% yield.
Example 8
Firstly, blowing and grinding black phosphorus crystals in a mortar by using argon gas until the black phosphorus crystals are powder with metal luster, transferring the black phosphorus powder into a beaker filled with the argon gas, adding a proper amount of water into the beaker, and preparing a black phosphorus dispersion liquid with the concentration of 1 mg/ml. Placing the beaker in an ice bath, placing the beaker into a cell crusher, under the argon atmosphere, enabling the bottom of a sample to be about 2cm away from an ultrasonic probe, enabling the ultrasonic power to be 80%, working for 8 hours in a mode of ultrasonic on for 2s and ultrasonic off for 4s, centrifuging for 10 minutes at the rotating speed of 7000r/min, and then freeze-drying for 3 hours at the temperature of 50 ℃ below zero to obtain the black phosphorus alkene;
secondly, ultrasonically dispersing 75mg of the black phosphorus alkene obtained in the first step into 40ml of isopropanol, wherein the ultrasonic power is 95%, and the ultrasonic time is 30 minutes; then adding 8ml of glycerol into the isopropanol dispersion liquid of the black phosphorus alkene, mechanically stirring at 250rpm/min for 1 hour to prepare the black phosphorus alkene dispersion liquid, wherein the whole process needs the protection of argon atmosphere;
thirdly, adding the total amount (4.5mmol) of Cu (NO) into the black phosphorus alkene dispersion liquid obtained in the second step3)2·6H2O and Co (NO)3)2·6H2O (the molar ratio is 1.0:3.5), mechanically stirring at 250rpm/min for 0.2 hour, transferring into a 100mL autoclave containing tetrafluoroethylene, heating at 160 ℃ for 6 hours, cooling to room temperature after the reaction is finished, washing with deionized water for multiple times, and freezing at-80 ℃ for 3 hours to obtain the nanocomposite;
fourthly, placing the nano composite material obtained in the third step into a quartz tube of a tube furnace, firstly pumping the nano composite material into a vacuum state by using a vacuum pump, then introducing argon to further exhaust air, repeating the process for 3 times, then heating to 450 ℃ at the speed of 5 ℃/min, and calcining at high temperature for 300min to obtain the nano composite materialObtaining PN/Cu/CoCuP2O7The yield of the product of the nano composite material is 93.5 percent.
Example 9
Firstly, blowing and grinding black phosphorus crystals in a mortar by using argon gas until the black phosphorus crystals are powder with metal luster, transferring the black phosphorus powder into a beaker filled with the argon gas, adding a proper amount of water into the beaker, and preparing a black phosphorus dispersion liquid with the concentration of 1 mg/ml. Placing the beaker in an ice bath, placing the beaker into a cell crusher, under the argon atmosphere, enabling the bottom of a sample to be about 2cm away from an ultrasonic probe, enabling the ultrasonic power to be 85%, working for 8 hours in a mode of ultrasonic on for 2s and ultrasonic off for 4s, centrifuging for 10 minutes at a rotating speed of 8000r/min, and then freeze-drying for 5 hours at the temperature of minus 40 ℃ to obtain the black phosphorus alkene;
secondly, ultrasonically dispersing 90mg of the black phosphorus alkene obtained in the first step in 40ml of methanol, wherein the ultrasonic power is 95%, and the ultrasonic time is 30 minutes; then adding 8ml of glycerol into the isopropanol dispersion liquid of the black phosphorus alkene, mechanically stirring at 250rpm/min for 1 hour to prepare the black phosphorus alkene dispersion liquid, wherein the whole process needs the protection of argon atmosphere;
thirdly, adding the total amount (4.5mmol) of Cu (NO) into the black phosphorus alkene dispersion liquid obtained in the second step3)2·6H2O and Co (NO)3)2·6H2O (the molar ratio is 1.0:3.5), mechanically stirring at 250rpm/min for 0.2 hour, transferring into a 100mL autoclave containing tetrafluoroethylene, heating at 160 ℃ for 6 hours, cooling to room temperature after the reaction is finished, washing with deionized water for multiple times, and freezing at-80 ℃ for 3 hours to obtain the nanocomposite;
fourthly, placing the nano composite material obtained in the third step into a quartz tube of a tube furnace, firstly pumping the nano composite material into a vacuum state by using a vacuum pump, then introducing argon to further exhaust air, repeating the process for 3 times, then heating the nano composite material to 450 ℃ at the speed of 5 ℃/min, and calcining the nano composite material at high temperature for 300min to obtain PN/Cu/CoCuP2O7The yield of the product of the nano composite material is 93.5 percent.
Example 10
Firstly, blowing and grinding black phosphorus crystals in a mortar by using argon gas until the black phosphorus crystals are powder with metal luster, transferring the black phosphorus powder into a beaker filled with the argon gas, adding a proper amount of water into the beaker, and preparing a black phosphorus dispersion liquid with the concentration of 1 mg/ml. Placing the beaker in an ice bath, placing the beaker into a cell crusher, under the argon atmosphere, enabling the bottom of a sample to be about 2cm away from an ultrasonic probe, enabling the ultrasonic power to be 95%, working for 8 hours in a mode of ultrasonic on for 2s and ultrasonic off for 4s, centrifuging for 10 minutes at a rotating speed of 9000r/min, and then freeze-drying for 10 hours at a temperature of-10 ℃ to obtain the black phosphorus alkene;
secondly, ultrasonically dispersing 80mg of the black phosphorus alkene obtained in the first step in 40ml of ethanol, wherein the ultrasonic power is 95%, and the ultrasonic time is 30 minutes; then adding 8ml of glycerol into the isopropanol dispersion liquid of the black phosphorus alkene, mechanically stirring at 250rpm/min for 1 hour to prepare the black phosphorus alkene dispersion liquid, wherein the whole process needs the protection of argon atmosphere;
thirdly, adding the total amount (4.5mmol) of Cu (NO) into the black phosphorus alkene dispersion liquid obtained in the second step3)2·6H2O and Co (NO)3)2·6H2O (the molar ratio is 1.0:3.5), mechanically stirring at 250rpm/min for 0.2 hour, transferring into a 100mL autoclave containing tetrafluoroethylene, heating at 160 ℃ for 6 hours, cooling to room temperature after the reaction is finished, washing with deionized water for multiple times, and freezing at-80 ℃ for 3 hours to obtain the nanocomposite;
fourthly, placing the nano composite material obtained in the third step into a quartz tube of a tube furnace, firstly pumping the nano composite material into a vacuum state by using a vacuum pump, then introducing argon to further exhaust air, repeating the process for 3 times, then heating the nano composite material to 450 ℃ at the speed of 5 ℃/min, and calcining the nano composite material at high temperature for 300min to obtain PN/Cu/CoCuP2O7The yield of the product of the nano composite material is 93.5 percent.
Experimental example 1
The PN/Cu/CoCuP prepared in the above example 12O7The nanocomposite is uniformly mixed with Ammonium Perchlorate (AP) according to the proportion of 1%, 3% and 5% and is used for TGA-DSC test, and the performance test results are shown in the following table 1:
TABLE 1
Test example
Example 1 nanocomposite
Ammonium perchlorate
Pyrolysis temperature (. degree.C.)
Exotherm (J/g)
1
0％
100 portions of
424.5
430.64
2
1％
100 portions of
344.6
1326.24
3
3％
100 portions of
323.9
2421.74
4
5％
100 portions of
303.9
2856.04
The PN/Cu/CoCuP of the embodiment 1 of the invention is added into the AP2O7Nano composite materialAfter the catalyst is fed, the high-temperature decomposition temperature of AP is reduced, the total heat release is increased, the catalytic effect is obviously improved, and the catalytic performance is also increased along with the increase of the addition amount of the nano composite material.
Experimental example 2
The PN/Cu/CoCuP prepared in the above example 22O7The nanocomposite material was mixed with explosive hexogen (RDX) in proportions of 1%, 3% and 5% for TGA-DSC testing, with the following performance test results in table 2 below:
TABLE 2
Test example
Example 2 nanocomposite
Explosive hexogen
Pyrolysis temperature (. degree.C.)
Exotherm (J/g)
1
0％
100 portions of
259.35
2812.38
2
1％
100 portions of
255.0
2998.78
3
3％
100 portions of
253.07
3040.89
4
5％
100 portions of
243.65
3777.42
The PN/Cu/CoCuP of the embodiment 2 of the invention is added into RDX2O7After the nano composite material is prepared, the high-temperature decomposition temperature of RDX is reduced, the total heat release is increased, the catalytic effect is obviously improved, and the catalytic performance is also increased along with the increase of the addition amount of the nano composite material.
Experimental example 3
The PN/Cu/CoCuP prepared in the above example 32O7The nano composite material is uniformly mixed with hexanitrohexaazaisopentane (CL-20) according to the proportion of 1%, 3% and 5%, and is used for TGA-DSC test, and PN/Cu/CoCuP of embodiment 3 of the invention is added into the CL-202O7After the nano composite material is adopted, the high-temperature decomposition temperature of CL-20 is reduced, the total heat release is increased, the catalytic effect is obviously improved, the catalytic performance is also increased along with the increase of the addition amount of the nano composite material, and the effect is the same as that of experimental example 2.
Comparative example
The method of example 1 is used to prepare the nanocomposite, except that the preparation process is carried out in air without adding protective gas, and the porous spherical nanocomposite with a smooth surface is obtained, compared with the spherical nanocomposite with protrusions and non-smooth surface which is obtained in an inert atmosphere, the spherical nanocomposite with protrusions and non-smooth surface has few surface active sites, is not beneficial to contact with the surface of an energetic material, and has poor catalytic effect, and the comparative results of the morphology of the nanocomposite obtained by calcination in different atmospheres are shown in figure 1.
From the above embodimentsThe invention provides a PN/Cu/CoCuP2O7The method comprises the steps of firstly carrying out stripping treatment on black phosphorus crystals by using a liquid phase stripping method, then carrying out treatment by using a hot solvent method, washing and drying to obtain the nano composite material, and finally calcining under a protective atmosphere to obtain the PN/Cu/CoCuP2O7A nanocomposite material. The invention has simple preparation process, easy process control and high product yield, and the prepared PN/Cu/CoCuP2O7The nano composite material not only can control the formation of phase, the size and the form of particle diameter, but also has large specific surface area and good electrical conductivity and thermal conductivity of the black phosphorus alkene (PN), and the existence of the PN can inhibit Cu and CoCuP2O7The particles agglomerate and at the same time the thermal conductivity can be increased.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.