CN114853052A - Oxygen-deficient cuprous oxide nano combustion catalyst, preparation method and application thereof - Google Patents
Oxygen-deficient cuprous oxide nano combustion catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an oxygen-deficient cuprous oxide nano combustion catalyst, a preparation method and application thereof. The preparation method comprises the steps of hydrolyzing a copper-amine complex solution to prepare Cu 2 O 1‑x Precursor, and adding the Cu 2 O 1‑x And (3) calcining the precursor in vacuum to prepare the oxygen-deficient cuprous oxide nano combustion catalyst. The oxygen-deficient cuprous oxide nano combustion catalyst can be used as a combustion catalyst for a solid propellant. The preparation method of the oxygen-deficient cuprous oxide nano combustion catalyst comprises the step of vacuum calcining Cu 2 O 1‑x Precursor, adding Cu 2 O 1‑x Oxygen vacancy defect in the precursor, thereby improving the combustion catalytic activity of the oxygen-deficient cuprous oxide nano combustion catalyst. The oxygen-deficient cuprous oxide nano combustion catalyst is used as a combustion catalyst in a solid propellant, so that the combustion speed of the solid propellant under low pressure can be remarkably improved, and the combustion speed pressure index, laser ignition energy and ignition delay time of the solid propellant are reduced.
Description
Technical Field
The invention belongs to the technical field of solid propellants, relates to a solid propellant combustion catalyst, and particularly relates to an oxygen-deficient cuprous oxide nano combustion catalyst, a preparation method and application thereof.
Background
The composite solid propellant is widely applied to tactical missile and weapon systems as a main power source, and the comprehensive performance of the composite solid propellant directly influences the damage capability, the striking precision and the survival capability of modern weapon systems. The combustion performance is the core of the solid propulsion technology, and the burning rate and the pressure index are two important indexes for measuring the combustion performance of the propellant. The oxidizer is the main energy component of the composite solid propellant, the ammonium perchlorate is the most commonly used oxidizer in the composite solid propellant, the content of the oxidizer in the composite solid propellant is more than 60 wt%, and the thermal decomposition performance of the oxidizer has important influence on the combustion performance of the solid propellant.
The use of combustion catalysts is the best way to adjust the combustion performance of solid propellants, and the main functions are as follows: (1) the ignition performance of the propellant is improved; (2) designing a thrust scheme according to the actual application requirement, and adjusting the burning speed of the propellant; (3) changing the reaction speed of the propellant during low-pressure combustion; (4) the combustion stability of the propellant is improved; (5) the sensitivity of the burning rate of the propellant on the influence of pressure and temperature is reduced. The nanometer combustion catalyst has small particle size, large specific surface area, many surface atoms, complex microstructure of crystal grains and various lattice defects, so the nanometer combustion catalyst has higher combustion catalytic activity and becomes one of the hot spots of research in the field of explosives and powders.
Currently, the nano-combustion catalysts used in propellants mainly include metal oxides, inert organometallic complexes, metal complexes, energetic compounds, and the like. Wherein, the nanometer cuprous oxide (Cu) 2 O) is attracting attention due to its ideal semiconductor properties, good catalytic properties and advantages of low toxicity, high storage capacity, low cost, etc., which not only promotes thermal decomposition of the oxidizer and improves the ballistic performance of the composite propellant, but also regulates the burning rate and pressure index of the solid propellant.
In recent years, researchers have conducted a lot of beneficial researches on the aspect of improving the combustion catalytic activity of nano cuprous oxide. Luo et al reported ammonium perchlorate with porous Cu 2 After O is mixed, the low-temperature decomposition peak temperature and the high-temperature decomposition peak temperature of the ammonium perchlorate are respectively reduced by 37 ℃ and 71 ℃. Chenyashao group studied Cu with cubic, octahedral and hollow sphere structure 2 The catalytic activity of O on the thermal decomposition reaction of ammonium perchlorate, and researches show that Cu 2 The catalytic activity of O in the thermal decomposition reaction of ammonium perchlorate is closely related to the structure of O. Research on Cu in Tang-Yi-Wen team 2 O shows morphology-dependent catalytic activity in different stages of ammonium perchlorate thermal decomposition.
However, the current research on improving the combustion catalytic activity of nano cuprous oxide mainly focuses on Cu 2 The particle size, morphology, surface structure and crystal face effect of O have limited effect on improving combustion catalytic activity and lack of research on influence on crystal defects, especially oxygen vacancy defects. Further, with respect to Cu 2 The influence of the O structure defect on the combustion catalytic performance is rarely reported, which limits the further improvement of the catalytic activity of the solid propellant combustion catalyst, and further causes the difficulty in meeting the technical requirement of accurately regulating and controlling the combustion performance of the solid propellant.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an oxygen-deficient cuprous oxide nano combustion catalyst and a preparation method thereof, and solve the technical problem that the combustion catalytic activity of the cuprous oxide nano combustion catalyst in the prior art is further improved.
In view of the defects in the prior art, another object of the present invention is to provide an application of the oxygen-deficient cuprous oxide nano-combustion catalyst as a combustion catalyst in a solid propellant, so as to solve the technical problem that the catalyst in the prior art cannot meet the technical requirement of accurately regulating and controlling the combustion performance of the solid propellant.
In order to solve the technical problems, the invention adopts the following technical scheme:
a process for preparing the cuprous oxide as the oxygen-deficient nano-class combustion catalyst includes such steps as preparing the Cu-Cu catalyst 2+ ) Coordinating with organic amine to prepare copper-amine complex, and hydrolyzing the copper-amine complex to obtain Cu 2 O 1-x Precursor, and adding the Cu 2 O 1-x After the precursor is calcined in vacuum, the oxygen-deficient cuprous oxide nano combustion catalyst is prepared;
the calcining conditions are as follows: adding the Cu 2 O 1-x And placing the precursor in a vacuum environment, heating to 100-300 ℃ at a heating rate of 5-20 ℃/min, and calcining at 100-300 ℃ for 2-4 h to prepare the oxygen-deficient cuprous oxide nano combustion catalyst.
The invention also has the following technical characteristics:
specifically, the preparation process of the copper-amine complex solution comprises the following steps: adding a copper salt into an aprotic polar solvent, heating to 50-90 ℃, stirring until the copper salt solid is completely dissolved to prepare a solution A, and adding an organic amine ligand to prepare a solution B; and centrifuging the solution B to obtain a supernatant, namely the copper-amine complex solution.
Specifically, Cu in the solution A 2+ The final concentration of (a) is 0.05-0.3 mol/L.
Specifically, the solution B contains organic amine ligand and Cu 2+ The molar ratio of (3-20): 1.
specifically, the organic amine ligand is ethylenediamine, diethylamine, triethylamine or ethylamine; the copper salt is copper sulfate, copper chloride, copper acetate or copper nitrate; the aprotic polar solvent is tetrahydrofuran, dichloromethane, acetonitrile, propionitrile, acetone or N, N-dimethylformamide.
Specifically, the Cu 2 O 1-x The preparation process of the precursor comprises the following steps: heating the copper-amine complex solution to 50-90 ℃, and then adding water preheated to the same temperature to prepare a mixed solution C; standing the mixed solution C at 50-90 ℃ for reaction, centrifuging to collect precipitate D, and freeze-drying the precipitate D to obtain Cu 2 O 1-x And (3) precursor.
The invention also discloses an oxygen-deficient cuprous oxide nano combustion catalyst, which is prepared by adopting the preparation method of the oxygen-deficient cuprous oxide nano combustion catalyst.
The invention also protects the application of the oxygen-deficient cuprous oxide nano combustion catalyst prepared by the preparation method of the oxygen-deficient cuprous oxide nano combustion catalyst as a combustion catalyst in a solid propellant.
Specifically, the oxygen-deficient cuprous oxide nano combustion catalyst is added into a solid propellant to prepare a composite solid propellant; the addition amount of the oxygen-deficient cuprous oxide nano combustion catalyst is 0.5-2% of the mass of the solid propellant.
Specifically, the burning rate of the composite solid propellant containing the oxygen-deficient cuprous oxide nano combustion catalyst in a pressure intensity range of 4-7 MPa is 8-11 mm/s, the burning rate pressure index in the pressure intensity range of 4-15 MPa is less than or equal to 0.38, and the burning rate pressure index in the pressure intensity range of 70W/cm 2 The laser ignition delay time under the laser power density is less than or equal to 256ms and is 95.4W/cm 2 The laser ignition delay time under the laser power density is less than or equal to 131 ms.
Compared with the prior art, the invention has the following technical effects:
the preparation method of the oxygen defect state cuprous oxide nano combustion catalyst of the invention comprises the steps of vacuum calcination of Cu 2 O 1-x Precursor, adding Cu 2 O 1-x The oxygen vacancy defect concentration in the precursor can effectively regulate the surface structure and electronic structure of the catalyst,promotes the chemical adsorption of the reaction intermediate on the surface of the catalyst, and further improves the combustion catalytic activity of the oxygen-deficient cuprous oxide nano combustion catalyst.
(II) the preparation method of the oxygen-deficient cuprous oxide nano combustion catalyst adopts the raw materials which are all low in price and easy to obtain. The preparation method has the advantages of simple process, strong controllability, mild preparation conditions, low energy consumption, and economic and environmental friendliness.
(III) the micro-morphology of the oxygen-deficient cuprous oxide nano combustion catalyst prepared by the invention is a spherical nano catalyst with uniform particle size distribution and good dispersibility, namely Cu 2 O 1-x The crystal lattice contains rich oxygen vacancy defects and has excellent combustion catalytic activity.
(IV) the oxygen-deficient cuprous oxide nano combustion catalyst is used as a combustion catalyst in a solid propellant, so that the combustion speed of the solid propellant under low pressure (4-7 MPa) can be remarkably improved, the combustion speed pressure index of the solid propellant in a pressure intensity range of 4-15 MPa is reduced, the laser ignition energy and the ignition delay time of the solid propellant under low laser power density are reduced, the dosage of the catalyst in a solid propellant formula is reduced, and the energy level of the solid propellant is improved.
Drawings
FIG. 1 is an XRD spectrum of an oxygen deficient cuprous oxide nano-combustion catalyst of example 2; in FIG. 1, a represents an oxygen-deficient cuprous oxide nano-combustion catalyst, and b represents Cu in standard card JCPDS No.05-0667 2 O。
Fig. 2 is an SEM image of the oxygen deficient cuprous oxide nano-combustion catalyst of example 2.
Fig. 3 is a graph showing the particle size distribution of the oxygen deficient cuprous oxide nano-combustion catalyst of example 2.
FIG. 4(a) shows an oxygen-deficient cuprous oxide nano-combustion catalyst, Cu 2 O 1-x Precursor and commercial Cu 2 A comparison graph of XPS spectra of O nano-catalysts; in FIG. 4(a), "Cu 2 O' represents commercial Cu 2 O nano catalyst,' Cu 2 O 1-x Precursor "represents Cu 2 O 1-x Precursor, "Cu 2 O 1-x "represents the oxygen-deficient cuprous oxide nano combustion catalyst.
FIG. 4(b) is commercial Cu in comparative example 1 2 XPS spectrum of O nano catalyst.
FIG. 4(c) shows Cu in comparative example 2 2 O 1-x XPS spectrum of the precursor.
Fig. 4(d) is an XPS spectrum of the oxygen deficient cuprous oxide nano-combustion catalyst of example 2.
Fig. 5 is a HRTEM of the oxygen deficient cuprous oxide nano-combustion catalyst of example 2.
FIG. 6 shows an oxygen-deficient cuprous oxide nano-combustion catalyst and commercial Cu 2 ESR spectrogram of the O nano catalyst; in FIG. 6, "Cu 2 O' represents commercial Cu 2 O nano catalyst,' Cu 2 O 1-X "indicates an oxygen-deficient cuprous oxide nano-combustion catalyst.
FIG. 7 is a DSC chart of the thermal decomposition reaction of ammonium perchlorate; in FIG. 7, "pure AP" means pure ammonium perchlorate without any catalyst, and "AP + Cu" means 2 O "represents addition of commercial Cu 2 Ammonium perchlorate of O nano catalyst, "AP + Cu 2 O 1-x Precursor "means that Cu is added 2 O 1-x Ammonium perchlorate of precursor, "AP + Cu 2 O 1-x "indicates ammonium perchlorate with added oxygen deficient cuprous oxide nano-burn catalyst.
FIG. 8 is a graph showing the burning rate at different pressures in the application example; in FIG. 8, "KB" represents the composite solid propellant, "KB + 0.5% Cu 2 O 1-x "represents a composite solid propellant containing 0.5% of cuprous oxide nano-combustion catalyst in oxygen deficient state.
FIG. 9 is a graph of the ignition delay time test at different laser power densities in the application example; in FIG. 9, "KB" represents the composite solid propellant, "KB + 0.5% Cu 2 O 1-x "represents a composite solid propellant containing 0.5% of cuprous oxide nano-combustion catalyst in oxygen deficient state.
The present invention will be explained in further detail with reference to examples.
Detailed Description
Based on the current situation in the background technology, the invention applies a defect engineering strategy, and the crystal structure defect is constructed by a scientific means, so that the oxygen defect state cuprous oxide nano combustion catalyst is prepared, the combustion catalysis performance of the nano metal oxide is substantially improved, the thermal decomposition efficiency of ammonium chlorate is improved, and the requirement of accurately regulating and controlling the combustion performance of the solid propellant is further met.
It is to be noted that all the raw materials in the present invention, unless otherwise specified, may be those known in the art. For example: the composite solid propellant adopts the composite solid propellant which is known in the prior art and takes ammonium perchlorate as an oxidizer.
In the present invention, Cu 2 O 1-x Refers to cuprous oxide in oxygen defect state, wherein x is more than 0 and less than 1.
The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.
Example 1:
the embodiment provides a preparation method of an oxygen-deficient cuprous oxide nano combustion catalyst, which specifically comprises the following steps:
preparing a copper-ethylenediamine complex;
adding 400mL of acetonitrile into a round-bottom flask, then weighing 0.06mol of copper chloride, adding the weighed copper chloride into an acetonitrile solvent under the stirring condition, heating the mixture to 75 ℃ in an oil bath, and continuously stirring until the copper chloride solid is completely dissolved to prepare a solution A, wherein Cu in the solution A is 2+ The final concentration of (A) is 0.15 mol/L; adding 0.36mol of ethylenediamine into the solution A to prepare a solution B, wherein the ethylenediamine and the Cu in the solution B 2+ In a molar ratio of 4: 1; and heating and stirring the solution B for 1-2 h, naturally cooling to room temperature, centrifuging at a high speed, removing solid precipitate, and transferring supernatant obtained by centrifuging to a round-bottom flask to obtain the copper-ethylenediamine complex solution.
Step two, Cu 2 O 1-x Preparing a precursor;
heating the copper-ethylenediamine complex solution prepared in the step one to 75 ℃, pouring deionized water preheated to 75 ℃ after 5min to prepare a mixed solution C, wherein the volume ratio of the deionized water to the copper-ethylenediamine complex solution is 1: 1; and (3) standing the solution C for reaction for 4 hours under the heating condition of 75 ℃, naturally cooling to room temperature, centrifuging to collect precipitate D, washing the precipitate D three times by using a mixed solution of acetone and acetonitrile, wherein the volume ratio of the acetone to the acetonitrile in the mixed solution is 1: 1, after washing, carrying out freeze drying for 12h to obtain Cu 2 O 1-x And (3) precursor.
Step three, preparing an oxygen-deficient cuprous oxide nano combustion catalyst;
cu collected in the second step 2 O 1-x The precursor is placed in a closed tube furnace, the precursor is heated to 200 ℃ from room temperature at the heating rate of 5 ℃/min under the vacuum condition, the precursor is calcined at 200 ℃ for 3h and then is naturally cooled to room temperature, and the product is collected to prepare the oxygen defect state cuprous oxide nano combustion catalyst.
Example 2:
the embodiment provides a preparation method of an oxygen-deficient cuprous oxide nano combustion catalyst, which specifically comprises the following steps:
step one, preparing a copper-triethylamine complex;
adding 400mL of N, N-Dimethylformamide (DMF) into a round-bottom flask, then weighing 0.06mol of copper chloride, adding the weighed copper chloride into a DMF solvent under the condition of stirring, heating the mixture to 85 ℃ in an oil bath, and continuously stirring until the copper chloride solid is completely dissolved to prepare a solution A, wherein Cu in the solution A is dissolved 2+ The final concentration of (A) is 0.15 mol/L; then adding 0.36mol of triethylamine to prepare a solution B, wherein triethylamine and Cu are in the solution B 2+ In a molar ratio of 6: 1; and heating and stirring the solution B for 1-2 h, naturally cooling to room temperature, centrifuging at a high speed, removing solid precipitate, transferring supernatant obtained by centrifuging to a round-bottom flask, and thus obtaining the copper-triethylamine complex solution.
Step two, Cu 2 O 1-x Preparing a precursor;
heating the copper-triethylamine complex solution prepared in the step one to 85 ℃, pouring deionized water preheated to 85 ℃ after 5min to prepare a mixed solution C, wherein the volume ratio of the deionized water to the copper-triethylamine complex solution is 1: 1. and (3) standing the solution C under the heating condition of 85 ℃ for reaction and precipitating for 4 hours, naturally cooling to room temperature, and centrifuging to collect orange yellow precipitate D. Washing the orange precipitate D three times by using a mixed solution of acetone and DMF, wherein the volume ratio of acetone to DMF in the mixed solution is 1: 1. after washing, freeze drying for 12h to obtain orange-yellow Cu 2 O 1-x And (3) precursor.
Step three, preparing an oxygen-deficient cuprous oxide nano combustion catalyst;
the orange-yellow Cu prepared in the step two 2 O 1-x And placing the precursor in a closed tube furnace, heating the precursor to 300 ℃ from room temperature at a heating rate of 5 ℃/min under a vacuum condition, calcining the precursor at 300 ℃ for 4 hours, naturally cooling the calcined precursor to room temperature, and collecting a product to obtain the orange-yellow oxygen-deficient cuprous oxide nano combustion catalyst.
The oxygen-deficient cuprous oxide nano combustion catalyst prepared in the embodiment is characterized as follows:
FIG. 1 is the XRD spectrum of the oxygen-deficient cuprous oxide nano-combustion catalyst in this example, the characteristic peak of crystal diffraction in FIG. 1 and Cu in standard card JCPDS No.05-0667 2 O is highly matched and there are no impurity peaks. Calculating to obtain Cu according to the XRD spectrogram and Scherrer equation 2 O 1-x The average grain size of the nanoparticles was 17.9 nm.
Fig. 2 is an SEM image of the oxygen-deficient cuprous oxide nano combustion catalyst in this example, and fig. 3 is a particle size distribution diagram of the oxygen-deficient cuprous oxide nano combustion catalyst in this example, and it can be seen from fig. 2 and 3 that the oxygen-deficient cuprous oxide nano combustion catalyst has a nano-spherical morphology with a uniform particle size distribution of about 203 ± 20 nm.
In this example, XPS spectra of the oxygen-deficient cuprous oxide nano-combustion catalyst are shown in fig. 4(a) and 4(d), and as can be seen from fig. 4(a) and 4(d), the main elements of the oxygen-deficient cuprous oxide nano-combustion catalyst are Cu and O elements, the valence of Cu in the oxygen-deficient cuprous oxide nano-combustion catalyst is +1, and the oxygen-deficient cuprous oxide nano-combustion catalyst contains a large number of oxygen vacancy defects.
FIG. 5 is a HRTEM image of the oxygen deficient cuprous oxide nano-combustion catalyst in this example, Cu in FIG. 5 2 O 1-x The nano-particles have clear lattice stripes with a plane spacing of 0.24nm and cubic phase Cu 2 The (111) crystal face of O is coincident. Further, Cu in FIG. 5 2 O 1-x Various crystal defects in the form of obvious lattice distortion, vacancies, dislocations and the like can also be seen in the lattice fringes of the nanoparticles.
In this example, the ESR spectrum of the oxygen-deficient cuprous oxide nano-combustion catalyst is shown in fig. 6, and as can be seen from fig. 6, the oxygen-deficient cuprous oxide nano-combustion catalyst contains a large number of oxygen vacancy defects.
The performance of the oxygen-deficient cuprous oxide nano-combustion catalyst of the present example was tested as follows:
in this embodiment, the oxygen-deficient cuprous oxide nano combustion catalyst is mixed with ammonium perchlorate in an amount of 0.5%, the combustion catalytic effect of the oxygen-deficient cuprous oxide nano combustion catalyst on ammonium perchlorate is tested, pure ammonium perchlorate is used as a blank control group during the test, and the test result is shown in fig. 7.
Application example:
the application example shows the application of the oxygen-deficient cuprous oxide nano combustion catalyst prepared by the preparation method of the oxygen-deficient cuprous oxide nano combustion catalyst described in example 2 as a combustion catalyst in a composite solid propellant.
As a specific scheme of the application example, the oxygen-deficient cuprous oxide nano combustion catalyst is added into a composite solid propellant to prepare the composite solid propellant containing the oxygen-deficient cuprous oxide nano combustion catalyst; the addition amount of the oxygen-deficient cuprous oxide nano combustion catalyst is 0.5 percent of the mass of the composite solid propellant.
The performance test of the composite solid propellant of the oxygen-containing defect-state cuprous oxide nano combustion catalyst in the application example is as follows:
in the application example, the composite solid propellant of the oxygen-containing defective cuprous oxide nano combustion catalyst is used as an experimental group, the composite solid propellant is used as a blank control group, the burning rate tests under different pressures are carried out, and the test result is shown in fig. 8. As can be seen from FIG. 8, compared with the blank control group, the burning rate of the experimental group in the pressure range of 4-7 MPa is improved by more than 30%, and the burning rate pressure index in the pressure range of 4-15 MPa is reduced from 0.60 to 0.38. The composite solid propellant has better combustion catalysis effect only by adding 0.5 percent of oxygen defect state cuprous oxide nano combustion catalyst.
In the application example, the composite solid propellant of the oxygen-containing defective cuprous oxide nano combustion catalyst is used as an experimental group, the composite solid propellant is used as a blank control group, ignition delay time tests are performed under different laser power densities, and the test result is shown in fig. 9. As can be seen from FIG. 9, under the same test conditions, the ignition delay time of the experimental group and the blank control group both showed a decreasing trend with the increase of the power density, and compared with the blank control group, the ignition delay time of the experimental group under the low laser power density was significantly shortened, the laser ignition energy was significantly reduced, and 70W/cm was obtained 2 The delay time of laser ignition at power density is reduced from 523ms to 256ms, 95.4W/cm 2 The laser ignition delay time at power density dropped from 207ms to 131 ms.
Comparative example 1:
this comparative example shows a commercial Cu 2 And (3) O nano catalyst.
Commercial Cu of this comparative example 2 The O nanocatalyst was characterized as follows:
in this comparative example, commercial Cu 2 XPS spectra of O nanocatalyst are shown in FIG. 4(a) and FIG. 4(b), and it can be seen from FIG. 4(a) and FIG. 4(b) that the commercial Cu 2 The main elements in the O nano catalyst are Cu, O and C elements, and the commercial Cu 2 The valence state of Cu in the O nano catalyst is +1, and the commercial Cu 2 The O nano catalyst does not contain oxygen vacancy defects.
In this comparative example, commercial Cu 2 The ESR spectrum of the O nano catalyst is shown in FIG. 6.
Commercial Cu of this comparative example 2 The performance of the O nanocatalyst was tested as follows:
in this comparative example, commercial Cu was used 2 The commercial Cu was tested with O nanocatalyst mixed with ammonium perchlorate at 0.5% addition 2 The combustion catalysis effect of the O nano catalyst on the ammonium perchlorate is shown in figure 7.
Comparative example 2:
the comparative example shows Cu 2 O 1-x Precursor of the Cu 2 O 1-x The precursor is Cu prepared in the second step of the embodiment 2 2 O 1-x And (3) precursor.
Cu of this comparative example 2 O 1-x The precursors were characterized as follows:
in this comparative example, Cu 2 O 1-x XPS spectra of the precursors are shown in FIGS. 4(a) and 4(c), and it can be seen from FIGS. 4(a) and 4(c) that the Cu is present 2 O 1-x The main elements in the precursor are Cu, O and C elements, and the Cu 2 O 1-x The valence state of Cu in the precursor is +1, and the Cu 2 O 1-x The precursor contains a small amount of oxygen vacancy defects.
Cu of this comparative example 2 O 1-x The performance of the precursor was tested as follows:
in this comparative example, Cu 2 O 1-x The Cu was tested by mixing the precursor with 0.5% of ammonium perchlorate 2 O 1-x The combustion catalytic effect of the precursor on ammonium perchlorate is shown in fig. 7.
From example 2, comparative example 1 and comparative example 2, it can be seen that:
under the same test conditions, compared with pure ammonium perchlorate of a blank control group, the two exothermic peaks of the example 2 are combined into a single exothermic peak, the heat release is more concentrated, the decomposition peak temperature is advanced by 127.1 ℃, and the exothermic peak temperature is further reduced from 439.3 ℃ to 312.2 ℃; commercial Cu of comparative example 1 2 O-nanocatalyst only pyrolyzes ammonium perchlorateThe peak temperature is advanced by 105.2 ℃, the peak temperature of the high-temperature decomposition is reduced from 439.3 ℃ to 334.1 ℃, and the peak temperature of the low-temperature decomposition is reduced from 298.8 ℃ to 285.2 ℃; cu of comparative example 2 2 O 1-x The precursor only leads the peak temperature of the ammonium perchlorate pyrolysis to be advanced by 100.9 ℃, and the peak temperature of the ammonium perchlorate pyrolysis is reduced from 439.3 ℃ to 338.4 ℃.
From the above analysis, it is known that Cu is commercially available 2 O nano catalyst and Cu 2 O 1-x Compared with the precursor, the oxygen-deficient cuprous oxide nano combustion catalyst prepared by the invention has stronger catalytic action on the ammonium perchlorate thermal decomposition reaction, can combine the high-temperature decomposition peak and the low-temperature decomposition peak of the ammonium perchlorate into one exothermic peak, concentrates the exothermic reaction, and promotes the cuprous oxide catalytic activity due to oxygen vacancy defects. Relatively commercial Cu 2 O nano catalyst and Cu 2 O 1-x As for the precursor, the oxygen-deficient cuprous oxide nano combustion catalyst has more obvious catalytic effect, and the catalytic efficiency of the catalyst is far higher than that of Cu which does not contain or contains a small amount of oxygen vacancy defects 2 And (3) an O catalyst.
Claims (10)
1. The preparation method of the oxygen-deficient cuprous oxide nano combustion catalyst is characterized in that a Cu-amine complex solution is hydrolyzed to prepare Cu 2 O 1-x Precursor, and adding the Cu 2 O 1-x Calcining the precursor to prepare the oxygen-deficient cuprous oxide nano combustion catalyst;
the calcining conditions are as follows: adding the Cu 2 O 1-x And placing the precursor in a vacuum environment, heating to 100-300 ℃ at a heating rate of 5-20 ℃/min, and calcining at 100-300 ℃ for 2-4 h to prepare the oxygen-deficient cuprous oxide nano combustion catalyst.
2. The method for preparing an oxygen-deficient cuprous oxide nano-combustion catalyst according to claim 1, wherein said copper-amine complex solution is prepared by the process comprising: adding a copper salt into an aprotic polar solvent, heating to 50-90 ℃, stirring until the copper salt solid is completely dissolved to prepare a solution A, and adding an organic amine ligand into the solution A to prepare a solution B; and centrifuging the solution B to obtain a supernatant, namely the copper-amine complex solution.
3. The method for preparing the oxygen-deficient cuprous oxide nano-combustion catalyst according to claim 2, wherein said Cu in solution A is Cu 2+ The final concentration of (a) is 0.05-0.3 mol/L.
4. The method for preparing an oxygen-deficient cuprous oxide nano-combustion catalyst according to claim 2, wherein organic amine ligand and Cu in solution B 2+ The molar ratio of (3-20): 1.
5. the method for preparing the oxygen-deficient cuprous oxide nano combustion catalyst according to claim 2, wherein said organic amine ligand is ethylenediamine, diethylamine, triethylamine or ethylamine; the copper salt is copper sulfate, copper chloride, copper acetate or copper nitrate; the aprotic polar solvent is tetrahydrofuran, dichloromethane, acetonitrile, propionitrile, acetone or N, N-dimethylformamide.
6. The method for preparing an oxygen deficient cuprous oxide nano-combustion catalyst as claimed in claim 1 wherein said Cu is 2 O 1-x The preparation process of the precursor comprises the following steps: heating the copper-amine complex solution to 50-90 ℃, and then adding water preheated to 50-90 ℃ to prepare a solution C; standing the solution C at 50-90 ℃ for reaction, centrifuging, collecting precipitate D, and freeze-drying the precipitate D to obtain Cu 2 O 1-x And (3) precursor.
7. An oxygen-deficient cuprous oxide nano combustion catalyst, characterized by being prepared by the method for preparing the oxygen-deficient cuprous oxide nano combustion catalyst according to any one of claims 1 to 6.
8. Use of the oxygen deficient cuprous oxide nanocombustion catalyst obtained by the process of making oxygen deficient cuprous oxide nanocombustion catalyst of any of claims 1 to 6 as combustion catalyst in solid propellant.
9. The use according to claim 8, wherein the oxygen deficient cuprous oxide nanocombustion catalyst is added to the composite solid propellant to produce a composite solid propellant containing the oxygen deficient cuprous oxide nanocombustion catalyst; the addition amount of the oxygen-deficient cuprous oxide nano combustion catalyst is 0.5-2% of the mass of the composite solid propellant.
10. The application of the composite solid propellant as claimed in claim 9, wherein the burning rate of the oxygen-containing defect-state cuprous oxide nano combustion catalyst in a pressure range of 4-7 MPa is 8-11 mm/s, the burning rate pressure index in the pressure range of 4-15 MPa is less than or equal to 0.38, and the burning rate pressure index in the pressure range of 70W/cm is less than or equal to 0.38 2 The laser ignition delay time under the laser power density is less than or equal to 256ms and is 95.4W/cm 2 The laser ignition delay time under the laser power density is less than or equal to 131 ms.
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