CN115925495A - Carbon nano tube filled carbonyl metal compound composite burning rate catalyst - Google Patents
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Images
Abstract
The invention discloses a carbon nano tube filled carbonyl metal compound nano composite burning rate catalyst, adding oxidized carbon nano tube into carbonyl metal compound Mo (CO) 6 、Cr(CO) 6 、W(CO) 6 、Fe 2 (CO) 9 、Mn 2 (CO) 10 In the saturated solution, the tube cavity of the oxidized carbon nano tube is filled with the carbonyl metal compound through ultrasonic treatment, so that the carbon nano tube filled carbonyl metal compound nano composite burning rate catalyst is obtained. The preparation method is simple, the metal carbonyl compound is stably restrained in the carbon nano tube by utilizing the nano-scale pore canal of the carbon nano tube, the dispersion degree and the thermal stability of the metal carbonyl compound are greatly improved, the metal carbonyl compound and the carbon nano tube also have the 'synergetic catalysis' effect, and the metal carbonyl compound is combinedThe material can be decomposed into nano metal oxide with extremely small particles during pyrolysis, so that the specific surface area of the composite burning rate catalyst is improved, and the combustion catalytic performance of each other is improved.
Description
Technical Field
The invention belongs to the technical field of solid propellants, and particularly relates to a series of carbon nanotube-filled carbonyl metal compound composite burning rate catalysts.
Background
The addition of burning rate catalyst in solid propellant is one of the main ways to regulate the burning performance of propellant, and burning rate catalyst is used to change the burning course of propellant chemically. The burning rate catalyst is an important component for regulating and improving the ballistic performance of the propellant and is also a key functional material in the formulation of the solid propellant. At present, the burning rate catalysts commonly used in composite solid propellants are mainly: transition metal oxides, transition metals, carbon materials, organometallic compounds, and the like.
With the continuous and intensive research, more and more catalysts are researched and applied to solid propellants, and Carbon Nanotubes (CNTs) begin to come into the field of researchers and are widely researched and applied. The carbon nano tube has a larger cavity structure and a larger specific surface area, and can provide a large number of active sites for catalytic reaction, so that the carbon nano tube has excellent performance in the catalytic reaction. Yuanzhi front et Al have shown that carbon nanotubes are added to aluminum-containing modified dual-base propellants, and introduce combustion surface heat into the solid phase of the propellants during combustion, thereby promoting thermal decomposition in the solid phase region, and improving the combustion rate of the propellants (Yuanzhi front, zhao Feng, song XiuTze et Al. The influence of carbon nanotubes on the combustion performance and mechanical properties of Al-CMDB propellants. Energetic materials, 2018,26 (12): 1019-1024.). In addition, the carbon nano tube improves the tensile strength and the elongation of the propellant due to the high strength and the high flexibility of the carbon nano tube and the entanglement effect of the carbon nano tube and the adhesive.
The carbon nanotube filled with metal, oxide and other matter can improve the electromagnetic performance, conducting performance, mechanical performance, catalytic performance, etc. and thus has wide application in catalyst field. Meanwhile, researches show that the transition metal and the transition metal oxide have good catalytic effect, and the aggregation phenomenon of the transition metal and the transition metal oxide in the catalytic process influences the utilization of the active center site. The carbon nano tube has extremely large specific surface area, and the combination of the carbon nano tube and the nano metal particles can solve the problems of easy agglomeration and difficult dispersion of the nano catalytic active substance in the preparation process.
A series of nanocomposites of carbon nanotubes with embedded cobalt and nickel Compounds were successfully prepared by ultrasonography in Fanghai et al and found to exhibit better catalytic activity in Ammonium Perchlorate (AP) pyrolysis but only increase the heat release of AP by 1742.72J/g (Fang H, xu R, yang L, et al. The furniture failure of carbon nanotubes-encapsulated cobalt complexes and the needle high efficiency catalyst in the thermal degradation of ammonium perchlorate and hexogen. Journal of Alloys and composites, 2022,928, 167134.); according to the Ruizhong theory, 12 kinds of copper salt are respectively filled into carbon Nano tubes to prepare a copper-based Nano composite material, and the AP is subjected to catalytic test, so that the copper-based Nano composite material has certain catalytic performance, but the prepared composite burning rate catalyst has the best effect, and the heat release is only increased by 1448.06J/g after the composite burning rate catalyst is added into the AP (Xu R, yang L, fang H, et al. Copper compounds in carbon Nano tubes as catalysts for thermal decomposition of energetic Applied Nano Materials,2022, 14942-14953). Although the burning rate catalysts prepared from the two catalysts have certain catalytic effect on the main component AP of the solid propellant, the exothermic quantity change is small.
Metal carbonyl complexes are a class of complexes formed by a transition metal and a ligand CO, also known as metal carbonyl compounds. Metal carbonyl compounds have a particularly important position in modern organic chemistry, both in theoretical research and in practical applications. In the chemical industry, olefins can be converted into commercially valuable products such as aldehydes, alcohols, and carboxylic acid derivatives, and carbonylation is one of the most important steps in the process of synthesizing olefins. Research shows that solid metal carbonyl compounds can be used as carbonyl sources to replace carbon monoxide to directly participate in carbonylation reactions, and the carbonylation reactions are greatly developed in the field of organic chemistry. With the research, metal carbonyl compounds are widely used in the research of modern organic synthesis reaction, especially in the synthesis of natural products, bio-organic chemistry and pharmaceutical chemistry.
In view of the above, in order to improve the combustion efficiency of the propellant, the selection of the combustion rate catalyst is important. The carbon nano tube has unique catalytic activity, and the application of the metal carbonyl compound in other fields proves that the metal carbonyl compound has better potential catalytic activity, so that the novel composite burning rate catalyst prepared by combining the metal carbonyl compound and the carbon nano tube becomes one of potential development directions in the field of catalytic materials.
Disclosure of Invention
The invention aims to provide the carbon nano tube filled carbonyl metal compound composite burning rate catalyst which is simple to prepare, can be produced in large scale and has good catalytic action.
Aiming at the purpose, the invention adopts the technical scheme that: adding the oxidized carbon nano tube into a saturated solution of a carbonyl metal compound, washing with a solvent corresponding to the saturated solution of the carbonyl metal compound after ultrasonic treatment, carrying out suction filtration, and drying to obtain the carbon nano tube filled carbonyl metal compound composite burning rate catalyst; wherein the metal carbonyl compound is Mo (CO) 6 、Cr(CO) 6 、W(CO) 6 、Fe 2 (CO) 9 、Mn 2 (CO) 10 Any one of them.
Mo (CO) mentioned above 6 The solvent corresponding to the saturated solution of (1) is benzene, cr (CO) 6 The saturated solution of (2) corresponds to a solvent of chloroform, W (CO) 6 The saturated solution of (A) corresponds to a solvent of tetrahydrofuran, fe 2 (CO) 9 The saturated solution of (A) is pyridine, mn 2 (CO) 10 The saturated solution of (2) corresponds to ethanol as the solvent.
The addition ratio of the carbon oxide nano tube to the saturated solution of the carbonyl metal compound is 8-12 mg/mL.
The temperature of the ultrasonic treatment is 20-30 ℃, the ultrasonic time is 20-30 h, the ultrasonic power is 600-800W, the drying temperature is 50-60 ℃, and the time is 4-8 h.
The oxidized carbon nanotube with two open ends is obtained by carrying out ultrasonic treatment on a multi-wall carbon nanotube by a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, and then settling, filtering, washing and drying. The pipe diameter of the multi-walled carbon nanotube is 4-80 nm, the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid solution is 3, the ultrasonic treatment temperature of the mixed acid solution is 20-30 ℃, the time is 4-6 h, the ultrasonic power is 200-400W, the settling time is 20-24 h, the drying temperature is 60-80 ℃, and the drying time is 20-24 h.
The invention has the following beneficial effects:
the invention combines five kinds of carbonyl metal compounds with the carbon nano tube, and utilizes the nanometer pore canal of the carbon nano tube to ensure that the carbonyl metal compounds are stably restrained in the carbon nano tube, thereby obtaining the novel nano composite burning rate catalyst. The composite burning rate catalyst greatly improves the thermal stability of the carbonyl metal compound, and in addition, the carbon nano tube has smaller aperture, so the dispersion degree of the carbonyl metal compound can be greatly improved by filling the carbonyl metal compound into the carbon nano tube. During pyrolysis, the carbonyl metal compound is decomposed into nano metal oxide with extremely small particles, the specific surface area of the composite burning rate catalyst is improved, and the carbonyl metal compound and the carbon nano tube also have a 'synergistic catalysis' effect, so that the combustion catalytic performance of each other can be improved by a direct, effective and simple method.
Drawings
Fig. 1 is a transmission electron microscope image of the carbon nanotube-filled molybdenum hexacarbonyl composite burn rate catalyst prepared in example 1.
FIG. 2 is a differential scanning calorimetry curve of AP to which 5% of the carbon nanotube-filled metal carbonyl compound composite burning rate catalysts prepared in examples 1 to 5 was added and pure AP.
FIG. 3 is a differential scanning calorimetry analysis curve of pure AP and AP with 5% of the carbon nanotube-filled molybdenum hexacarbonyl composite burn rate catalyst prepared in example 1, the carbon nanotube-loaded molybdenum hexacarbonyl composite burn rate catalyst prepared in comparative example 1, carbon nanotube oxide CNTs-1 having a tube diameter of 4-6 nm, carbon nanotube CNTs-2 having an untreated tube diameter of 4-6 nm, and pure molybdenum hexacarbonyl added respectively.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
Adding 200mg of multi-walled carbon nanotubes with the tube diameter of 4-6 nm into 15mL of mixed acid solution with the volume ratio of concentrated sulfuric acid to concentrated nitric acid being 3, carrying out ultrasonic treatment at 30 ℃ and the power being 300W for 4h to obtain black viscous solution, adding deionized water into the solution, stirring uniformly by using a glass rod, standing at room temperature and settling for 24h to see that obvious layering exists in a beaker, pouring out the transparent solution on the upper layer, adding deionized water again, and repeating the steps for multiple times to obtain black suspension. And (3) carrying out suction filtration and separation on the black suspension, repeatedly washing with deionized water until the pH value of the obtained black solid precipitate is neutral, transferring the black solid precipitate into a forced air drying oven, drying at 80 ℃ for 24h, and uniformly grinding to obtain the carbon oxide nanotube with openings at two ends. 100mg of carbon oxide nanotubes was added to 10mL of Mo (CO) 6 The saturated benzene solution is treated by ultrasonic for 30 hours at the temperature of 30 ℃ and the power of 800W, then is washed by benzene for 3 times and is filtered, the product is put in a drying oven for drying for 6 hours at the temperature of 60 ℃, and is taken out, the obtained black powder is carbon nano tube filled molybdenum hexacarbonyl composite combustion rate catalyst, which is marked as Mo (CO) 6 @ CNTs. As can be seen from fig. 1, molybdenum hexacarbonyl is filled in the carbon nanotubes and a small amount of molybdenum hexacarbonyl is also present between the walls of the multi-walled carbon nanotubes.
Example 2
In this example, the same volume of Cr (CO) is used 6 Saturated chloroform solution in place of Mo (CO) in example 1 6 The procedure of example 1 was repeated to obtain a black powder of carbon nanotube-filled chromium hexacarbonyl composite burn rate catalyst, designated as Cr (CO) 6 @CNTs。
Example 3
In this example, the same volume of W (CO) is used 6 Replacement of Mo (CO) in example 1 by a saturated tetrahydrofuran solution of 6 The other steps of the saturated benzene solution of (1) were the same as in example 1, and the obtained black powder was a carbon nanotube-filled tungsten hexacarbonyl composite burning rate catalyst, denoted as W (CO) 6 @CNTs。
Example 4
In this example, equal volume of Fe was used 2 (CO) 9 Replacement of Mo (CO) in example 1 by a saturated pyridine solution of 6 The other steps of the saturated benzene solution are the same as those in example 1, and the obtained black powder is a carbon nanotube-filled nonacarbonyl diiron composite burning rate catalyst which is marked as Fe 2 (CO) 9 @CNTs。
Example 5
In this example, the same volume of Mn is used 2 (CO) 10 Replacement of Mo (CO) in example 1 by saturated ethanol solution of (C) 6 The other steps of the saturated benzene solution are the same as those in example 1, and the obtained black powder is a carbon nanotube-filled decacarbonyl dimanganese composite burning rate catalyst, which is marked as Mn 2 (CO) 10 @CNTs。
Comparative example 1
Adding 100mg of untreated carbon nano tube with the tube diameter of 4-6 nm into 10mL of deionized water, carrying out ultrasonic treatment for 30h at the temperature of 30 ℃ and the power of 800W, carrying out suction filtration, adding the product into 10mL of saturated benzene solution of molybdenum hexacarbonyl, stirring for 24h at room temperature, carrying out suction filtration, drying for 6h at the temperature of 60 ℃ in an oven, wherein the obtained black powder is a carbon nano tube loaded molybdenum hexacarbonyl composite burning rate catalyst, and is marked as Mo (CO) 6 /CNTs。
In order to prove the beneficial effects of the invention, 5% of the carbon nanotube-filled carbonyl metal compound composite burning rate catalysts prepared in examples 1 to 5 were added to AP respectively to perform a combustion catalysis performance test, and the results are shown in fig. 2. Simultaneously, 5 percent of the carbon nano tube loaded molybdenum hexacarbonyl composite burning rate catalyst (Mo (CO) of comparative example 1) is added into AP respectively 6 CNTs), 5 percent of carbon oxide nanotubes CNTs-1 with the tube diameter of 4-6 nm, 5 percent of carbon nanotubes CNTs-2 with the tube diameter of 4-6 nm and 5 percent of pure molybdenum hexacarbonyl, and the results are shown in figure 3.
As can be seen from the view in figure 2,under the same conditions, when 5% of the carbon nanotube filled carbonyl metal compound composite burning rate catalyst prepared in examples 1 to 5 is added into the main component AP of the solid propellant, the peak temperature in the AP pyrolysis stage is respectively reduced from 420.4 ℃ to 339.8 ℃, 331.1 ℃, 334.9 ℃, 309.3 ℃ and 334.8 ℃, 80.6 ℃, 89.3 ℃, 85.5 ℃, 111.1 ℃ and 85.6 ℃, the apparent decomposition heat of the AP is respectively increased from 976.42J/g to 3881.05J/g, 3305.25J/g, 3559.30J/g, 3119.01J/g and 3226.15J/g, and respectively increased from 2904.63J/g, 2328.83J/g, 2582.88J/g, 2142.59J/g and 2249.73J/g, wherein the heat release amount of the carbon nanotube filled molybdenum hexacarbonyl for the AP pyrolysis catalysis is the highest. After 5% of the carbon nanotube-filled carbonyl metal compound composite burning rate catalyst prepared in examples 1 to 5 was added, the peak temperature of AP was greatly reduced, and the concentrated heat release phenomenon was exhibited at the pyrolysis stage, and the heat release was significantly increased, indicating that the composite burning rate catalyst of the present invention has a good combustion catalytic effect on thermal decomposition of AP, in which the carbon nanotube-filled molybdenum hexacarbonyl composite burning rate catalyst Mo (CO) prepared in example 1 was added 6 The @ CNTs have the best catalytic effect on AP thermal decomposition, when 5% of the carbon nano tube prepared in the embodiment 1 is added into the solid propellant main component AP and filled with the molybdenum hexacarbonyl composite combustion rate catalyst, the heat release is obviously improved to be nearly 4 times of that of pure AP, and the heat release of the rest embodiments is also better improved than that of the pure AP.
As can be seen from FIG. 3, under the same conditions, when 5% of the Mo (CO) prepared in comparative example 1 was added to the main component AP of the solid propellant 6 When the/CNTs is used as a catalyst, the peak temperature of the AP pyrolysis stage is reduced from 420.4 ℃ to 338.7 ℃, and the apparent decomposition heat of AP is increased from 976.42J/g to 3270.10J/g. In addition, the catalytic performance evaluation is carried out by directly adding the metal carbonyl compound and pure AP, and the pure metal carbonyl compound is found not to show an obvious catalytic effect on the AP; adding 5% of carbon nanotube oxide to catalyze the AP thermal decomposition process, reducing the peak temperature of the AP high-temperature decomposition stage from 420.4 ℃ to 331.4 ℃, increasing the apparent decomposition heat of AP from 976.42J/g to 3211.89J/g, adding 5% of carbon nanotube CNTs-2 to catalyze the AP thermal decomposition process, reducing the peak temperature of the AP high-temperature decomposition stage from 420.4 ℃ to 311.5 ℃, and catalyzing the apparent decomposition heat of APThe peak temperature can be obviously reduced by increasing from 976.42J/g to 2600.74J/g, but the heat release is smaller, and compared with the catalytic effects of the two carbon nanotubes, the catalytic effect of the oxidized carbon nanotube on AP is obviously better than that of the untreated carbon nanotube.
Claims (7)
1. A carbon nano tube filled carbonyl metal compound composite burning rate catalyst is characterized in that: adding the oxidized carbon nano tube into a saturated solution of a carbonyl metal compound, washing with a solvent corresponding to the saturated solution of the carbonyl metal compound after ultrasonic treatment, carrying out suction filtration, and drying to obtain the carbon nano tube filled carbonyl metal compound composite burning rate catalyst; wherein the metal carbonyl compound is Mo (CO) 6 、Cr(CO) 6 、W(CO) 6 、Fe 2 (CO) 9 、Mn 2 (CO) 10 Any one of them.
2. The carbon nanotube-filled metal carbonyl compound composite burn rate catalyst of claim 1, wherein: the oxidized carbon nanotube with two open ends is obtained by subjecting a multi-walled carbon nanotube to ultrasonic treatment by a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, and then settling, filtering, washing and drying.
3. The carbon nanotube-filled metal carbonyl compound composite burn rate catalyst of claim 2, wherein: the tube diameter of the multi-walled carbon nano tube is 4-80 nm, and the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid solution is 3.
4. The carbon nanotube-filled metal carbonyl compound composite burn rate catalyst of claim 2, wherein: the ultrasonic treatment temperature of the mixed acid solution is 20-30 DEG o C. The time is 4 to 6 hours, the ultrasonic power is 200 to 400W, the sedimentation time is 20 to 24 hours, and the drying temperature is 60 to 80 hours o C, drying for 20-24 h.
5. Carbon nanotube-filled metal carbonyl combination of claim 1The composite combustion rate catalyst is characterized in that: the temperature of the ultrasonic treatment is 20-30 DEG o C. The ultrasonic time is 20 to 30 hours, the ultrasonic power is 600 to 800W, and the drying temperature is 50 to 60 o C. The time is 4 to 8 hours.
6. The carbon nanotube-filled metal carbonyl compound composite burn rate catalyst of claim 1, wherein: the addition proportion of the saturated solution of the oxidized carbon nanotube and the carbonyl metal compound is 8-12 mg/mL.
7. The carbon nanotube-filled metal carbonyl compound composite burn rate catalyst of claim 1, wherein: the Mo (CO) 6 The solvent corresponding to the saturated solution of (1) is benzene, cr (CO) 6 The saturated solution of (2) corresponds to a solvent of chloroform, W (CO) 6 The saturated solution of (A) is tetrahydrofuran, fe 2 (CO) 9 The saturated solution of (A) is pyridine, mn 2 (CO) 10 The saturated solution of (2) corresponds to ethanol as the solvent.
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| US20060245996A1 (en) * | 2005-04-27 | 2006-11-02 | Peking University | Method of synthesizing single walled carbon nanotubes |
| CN101456079A (en) * | 2007-12-12 | 2009-06-17 | 北京化工大学 | Method of filling carbon nano tube with nano metal lead particles |
| CN108114713A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院大连化学物理研究所 | Carbon nanometer tube loaded type catalyst for oxidizing atmosphere and preparation method thereof |
| CN114956914A (en) * | 2022-05-17 | 2022-08-30 | 陕西师范大学 | Carbon nanotube/alpha-Fe 2 O 3 Nano composite burning rate catalyst |
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| US20060245996A1 (en) * | 2005-04-27 | 2006-11-02 | Peking University | Method of synthesizing single walled carbon nanotubes |
| CN101456079A (en) * | 2007-12-12 | 2009-06-17 | 北京化工大学 | Method of filling carbon nano tube with nano metal lead particles |
| CN108114713A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院大连化学物理研究所 | Carbon nanometer tube loaded type catalyst for oxidizing atmosphere and preparation method thereof |
| CN114956914A (en) * | 2022-05-17 | 2022-08-30 | 陕西师范大学 | Carbon nanotube/alpha-Fe 2 O 3 Nano composite burning rate catalyst |
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