CN115974631A - ZIF-67 embedded carbonyl metal composite burning rate catalyst - Google Patents
ZIF-67 embedded carbonyl metal composite burning rate catalyst Download PDFInfo
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- 239000011733 molybdenum Substances 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims description 8
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- 239000011651 chromium Substances 0.000 claims description 8
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- 238000000034 method Methods 0.000 claims description 6
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 239000002114 nanocomposite Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- -1 carbonyl metal compound Chemical class 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
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- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002153 concerted effect Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
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- 230000000052 comparative effect Effects 0.000 description 19
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a ZIF-67 embedded metal carbonyl composite burning rate catalyst, which is prepared by adding saturated solution of metal carbonyl compound in the preparation process of ZIF-67, stirring at room temperature, washing generated precipitate with methanol and solvent corresponding to the saturated solution of metal carbonyl compound, filtering, and drying. According to the invention, the metal carbonyl compound is packaged in the ZIF-67, and the ZIF-67 nanometer pore canal is utilized, so that the metal carbonyl compound is stably restrained in the pore canal, and the thermal stability of the metal carbonyl compound is greatly improved; in addition, as the inner diameter of the pore channel of the ZIF-67 is less than 2nm, the dispersion degree of the metal carbonyl compound can be greatly improved by embedding the metal carbonyl compound into the ZIF-67, so that the metal carbonyl compound is decomposed into nano metal oxide with extremely small particles during pyrolysis, the specific surface area of the catalyst is improved, and the metal carbonyl compound and cobalt ions in the ZIF-67 have a concerted catalysis effect, so that the combustion catalysis performance of each other can be improved. The preparation method of the catalyst is simple, convenient to amplify and has good market application prospect.
Description
Technical Field
The invention belongs to the technical field of solid propellants, and particularly relates to a series of ZIF-67 embedded carbonyl metal composite burning rate catalysts.
Background
The solid propellant is a solid mixture of energy and working medium for obtaining thrust of the solid rocket engine, contains substances of an oxidant and a reducing agent required by combustion and explosion chemical reactions, can be excited by proper energy under the condition of no oxygen supply outside, can generate regular combustion or explosion reactions, and quickly releases a large amount of high-temperature gas, thereby achieving the purposes of launching a projectile, propelling the rocket or generating blasting. Generally, solid propellants are classified into a double-base propellant, a composite propellant and a modified double-base propellant, and since up to about 90% of solid filler can be added in the manufacturing process of the composite solid propellant, the energy performance and the mechanical performance of the composite solid propellant are superior to those of the traditional double-base propellant, the research on the composite solid propellant is more and more extensive in the field of solid propellants at present.
The combustion performance regulator is an important component of the solid propellant, is an additive for regulating the combustion speed and the pressure index of the propellant through physical or chemical action, and the addition amount of the additive only accounts for 1 to 5 percent of the mass fraction of the propellant, but can well regulate the combustion speed and the pressure index. In recent years, with the progress of research, it has been found that a combustion catalyst catalyzes a reaction occurring on the surface of the catalyst, and the larger the specific surface area is, the better the catalytic effect is. The Metal-Organic Frameworks (MOFs) have large specific surface area, regular pore channel structure, high crystallinity and highly dispersed Metal active sites, which indicates that the MOFs material is a good potential combustion catalyst. MOFs compounds consisting of a central metal ion andthe components, the crystal structure, the micro-pore structure and the like of the organic ligand are easy to regulate and control, so that each physical and chemical property of the organic ligand is easy to regulate and optimize. ZIF-67 is made of Co 2+ And 2-methylimidazole, is a zeolite imidazole ester framework material with a rhombic dodecahedron structure, is mainly used in the fields of electrocatalytic oxidation reduction, photocatalysis, catalytic oxidation of toluene and the like, and shows excellent catalytic performance.
First synthesis of Ni (CO) by Mond in 1890 years 4 In the chemical synthesis aspect, the metal carbonyls are applied to catalyzing the carbon dioxide cycloaddition reaction, and replace gas carbon monoxide to participate in the carbonylation reaction and the intramolecular N heterocyclic ring reaction as a carbonyl source; in the aspect of material preparation, carbonyl metal is used as a precursor to prepare a functional material of the magnetic composite film, and a steel material is modified so as to improve the corrosion resistance of the steel material. The research of novel carbonyl composite materials by utilizing the characteristics of high purity, low thermal dissociation temperature, diversity of dissociation products and the like of the carbonyl metal intermediate compound is one of the hot points of the current material research, and has wide application prospects in the fields of aerospace, electronics, energy, chemical engineering and the like.
Because the nano organic metal salt contains organic groups, the nano organic metal salt shows certain lipophilicity, and improves the compatibility with the propellant component and the dispersibility in the propellant. In 2014, liu Xiaoming utilizes a solvothermal method to synthesize a series of VIB metal carbonyl cluster compounds by room temperature decarbonylation, a modified MOFs structure is further obtained by modifying a functional group of an organic ligand, and the application of the modified MOFs structure in aqueous phase catalysis and photochemistry is discussed (Liu Xiaoming, synthesis and application research of the VIB metal carbonyl cluster compounds, hunan university, 2014), so that the VIB metal carbonyl cluster compounds have a good application prospect in the field of photochemical catalysis. Wei Ye to Fe 2 (CO) 9 Filling ZIF-8, and calcining to obtain Fe 2 The research shows that the material has excellent redox activity and better durability, and provides a new idea for designing and developing the electrocatalyst (Wei Ye, shuangming Chen, yue Lin, et alChemistry,2019,11 (5): 2865-2878). However, the preparation method of the catalyst is limited to the field of electrocatalysis, has a small application range and is complex in synthesis method.
Disclosure of Invention
The invention aims to provide the ZIF-67 embedded carbonyl metal composite burning rate catalyst which is simple to prepare, can be produced in large quantities and has good catalytic action.
Aiming at the purposes, the technical scheme adopted by the invention is as follows: adding a saturated solution of a metal carbonyl compound in the process of preparing ZIF-67 by stirring cobalt nitrate and 2-methylimidazole serving as raw materials and methanol serving as a solvent at room temperature, washing the generated purple precipitate with the solvent corresponding to the saturated solution of the methanol and the metal carbonyl compound, performing suction filtration, and drying to obtain the ZIF-67 embedded metal carbonyl composite burning rate catalyst; the metal carbonyl compound is any one of molybdenum hexacarbonyl, chromium hexacarbonyl and tungsten hexacarbonyl.
In the ZIF-67 embedded metal carbonyl nanocomposite burn rate catalyst, the molar ratio of metal atoms of the metal carbonyl compound to Co atoms in the ZIF-67 is preferably 1:3-1:4.
The particle size of the ZIF-67 embedded carbonyl metal nano composite burning rate catalyst is 400-500 nm, and the ZIF-67 structure is reserved.
The solvent corresponding to the saturated solution of chromium hexacarbonyl is trichloromethane, the solvent corresponding to the saturated solution of molybdenum hexacarbonyl is benzene, and the solvent corresponding to the saturated solution of tungsten hexacarbonyl is tetrahydrofuran.
The invention has the following beneficial effects:
according to the invention, a metal carbonyl compound is combined with a ZIF-67 material, the metal carbonyl compound is dissolved and added in the synthesis process of the ZIF-67 material, the mixture is encapsulated in the ZIF-67 material, and the ZIF-67 nano-scale pore passage is utilized to stably restrain the metal carbonyl compound in the pore passage, so that a novel composite combustion rate catalyst is obtained, and the thermal stability of the metal carbonyl compound is greatly improved; in addition, because the inner diameter of the pore channel of the ZIF-67 is less than 2nm, the dispersion degree of the metal carbonyl compound can be greatly improved by embedding the metal carbonyl compound into the ZIF-67, so that the metal carbonyl compound can be decomposed into nano metal oxide with extremely small particles during pyrolysis, the specific surface area of the catalyst is improved, the metal carbonyl compound and cobalt ions in the ZIF-67 also have a 'concerted catalysis' effect, and the combustion catalysis performance of each other can be improved by a direct, effective and simple method.
Drawings
FIG. 1 is a transmission electron micrograph of pure ZIF-67.
FIG. 2 is a transmission electron microscope photograph of the ZIF-67 inline molybdenum hexacarbonyl composite burn rate catalyst prepared in example 1.
FIG. 3 is a thermogravimetric plot of the composite burn rate catalyst, pure chromium hexacarbonyl, tungsten hexacarbonyl, molybdenum hexacarbonyl, pure ZIF-67 prepared in examples 1-3.
FIG. 4 is a differential scanning calorimetry analysis curve of the difference between the cases where 1-5% of the ZIF-67 embedded molybdenum hexacarbonyl composite burn rate catalyst prepared in example 1 was added to AP, respectively, and pure AP.
FIG. 5 is a differential scanning calorimetry curve of AP with 3% of the composite burn rate catalyst prepared in examples 1 to 3 added to the AP and pure AP.
FIG. 6 is differential scanning calorimetry analysis curves of pure AP and AP to which 3% of the ZIF-67 embedded molybdenum hexacarbonyl composite burn rate catalyst prepared in example 1, the ZIF-67 composite material prepared in comparative example 1 with molybdenum hexacarbonyl supported on the surface, the ZIF-67 composite material filled with molybdenum hexacarbonyl prepared in comparative example 2, and the ZIF-67 composite material prepared in comparative example 3 with supported and filled with molybdenum hexacarbonyl were added, respectively.
FIG. 7 is a differential scanning calorimetry curve of pure AP and AP with 3% of the composite burn rate catalysts prepared in examples 1-3, moCo-N-C prepared in comparative example 4, crCo-N-C prepared in comparative example 5, and WCo-N-C prepared in comparative example 6, respectively.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
0.90g (3 mmol) of cobalt nitrate hexahydrate anddissolving 1.12g (13 mmol) of 2-methylimidazole in 20mL of methanol respectively, dissolving 0.21g (0.8 mmol) of molybdenum hexacarbonyl in 10mL of benzene, adding the three solutions into a beaker simultaneously, adding magnetons, sealing the bottleneck with a preservative film at room temperature, stirring for 24 hours at room temperature to enable the solutions to react fully, after the reaction is completed, performing suction filtration, washing with benzene and methanol, and drying at 50 ℃ for 5 hours to obtain purple powder, namely a ZIF-67 embedded molybdenum hexacarbonyl composite combustion rate catalyst (ZIF-67 @ Mo (CO) 6 ). As can be seen by comparing FIG. 1 and FIG. 2, ZIF-67@ Mo (CO) 6 The morphology characteristics of the regular rhombic dodecahedron of the ZIF-67 are still kept, and a certain crystal form structure is kept.
Example 2
Respectively dissolving 0.90g (3 mmol) of cobalt nitrate hexahydrate and 1.12g (13 mmol) of 2-methylimidazole in 20mL of methanol, dissolving 0.17g (0.8 mmol) of chromium hexacarbonyl in 10mL of trichloromethane, simultaneously adding the three solutions into a beaker, adding magnetons, sealing the mouth of the beaker by a preservative film at room temperature, stirring for 24 hours to enable the solution to react fully, after the reaction is completed, performing suction filtration, washing by the trichloromethane and the methanol, and drying at 50 ℃ for 5 hours to obtain purple powder, namely ZIF-67 embedded chromium hexacarbonyl composite burning rate catalyst (ZIF-67 @ Cr (CO) 6 )。
Example 3
Respectively dissolving 0.90g (3 mmol) of cobalt nitrate hexahydrate and 1.12g (13 mmol) of 2-methylimidazole in 20mL of methanol, dissolving 0.27g (0.8 mmol) of tungsten hexacarbonyl in 10mL of tetrahydrofuran, simultaneously adding the three solutions into a beaker, adding magnetons, sealing the mouth of the beaker by a preservative film at room temperature, stirring for 24 hours to fully react, after the reaction is completed, performing suction filtration, washing by the tetrahydrofuran and the methanol, drying for 5 hours at 50 ℃, and obtaining purple powder, namely ZIF-67 embedded tungsten hexacarbonyl composite burning rate catalyst (ZIF-67 @ W (CO) 6 )。
Comparative example 1
Adding 50mg ZIF-67 into 10mL saturated benzene solution of molybdenum hexacarbonyl, adding magneton, stirring at room temperature for 24h, vacuum filtering, drying at 50 deg.C for 5h to obtain purple powder as ZIF-67 surface loaded molybdenum hexacarbonyl composite combustion rate catalyst (ZIF-67/Mo (CO) 6 )。
Comparative example 2
Adding 50mg ZIF-67 to the mixtureAdding into 10mL saturated benzene solution of molybdenum hexacarbonyl, performing ultrasonic treatment at 30 deg.C and 720W for 10 hr, filtering, washing with benzene, drying at 50 deg.C for 5 hr to obtain purple powder, and filling ZIF-67 prepared by ultrasonic method with molybdenum hexacarbonyl composite combustion rate catalyst (ZIF-67% Mo (CO) 6 )。
Comparative example 3
Adding 50mg of ZIF-67 into 10mL of saturated benzene solution of molybdenum hexacarbonyl, carrying out ultrasonic treatment for 10h at 30 ℃ and 720W, carrying out suction filtration on the product, drying for 5h at 50 ℃, and obtaining purple powder which is ZIF-67 filled and loaded with molybdenum hexacarbonyl composite burning rate catalyst (ZIF-67) prepared by an ultrasonic method&Mo(CO) 6 )。
Comparative example 4
100mg of ZIF-67@ Mo (CO) prepared in example 1 6 Calcining for 2h at 500 ℃ in a nitrogen atmosphere to obtain black powder MoCo-N-C.
Comparative example 5
100mg of ZIF-67@ Cr (CO) prepared in example 2 was added 6 Calcining for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain black powder CrCo-N-C.
Comparative example 6
100mg of ZIF-67@ W (CO) prepared in example 3 was added 6 Calcining for 2h at 500 ℃ in a nitrogen atmosphere to obtain black powder WCo-N-C.
Comparing the thermogravimetric curves of the composite burning rate catalysts prepared in the above examples 1-3 with pure metal carbonyls and pure ZIF-67 (see FIG. 3), it can be found that the pure metal carbonyls have poor thermal stability, the weight loss rates of chromium hexacarbonyl, molybdenum hexacarbonyl and tungsten hexacarbonyl reach 100% at 94.15 ℃, 97.9 ℃ and 127.6 ℃ respectively, while the ZIF-67 has no obvious weight loss below 480 ℃, the weight loss rate at 600 ℃ is 45.58%, and the thermal stability is good. After the metal carbonyl compound is embedded into the ZIF-67, the thermal stability is greatly improved. ZIF-67@ Mo (CO) prepared in example 1 6 The weight loss is 9.86 percent at 100-503 ℃, the weight loss rate reaches 42.98 percent at 503-600 ℃ and the weight loss is 52.84 percent at 0-600 ℃; example 2 preparation of ZIF-67@ Cr (CO) 6 The weight loss is 15.03 percent at 100-220 ℃, no obvious weight loss exists at 220-400 ℃, the weight loss rate reaches 39.37 percent at 400-600 ℃, and the weight loss is 54.5 percent at 0-600 ℃; example 3 preparation of ZIF-67@W(CO) 6 The weight loss is 4.18 percent at 100-522 ℃, the weight loss rate reaches 43.69 percent at 522-600 ℃ and the weight loss is 47.87 percent at 0-600 ℃. Compared with the prior art, the ZIF-67 embedded metal carbonyl composite material has better thermal stability, solves the problem that the metal carbonyl compound is easy to dissociate at low temperature, and can be used as a burning rate catalyst to be better applied to a solid propellant.
To demonstrate the advantageous effects of the present invention, comparative combustion catalytic performance tests were conducted by adding 1 the catalysts prepared in examples 1 to 3 and comparative examples 1 to 3 and adding a single ZIF-67 and a single metal carbonyl compound to AP, respectively, and the results are shown in fig. 4 to 7. As can be seen from FIG. 4, the exotherm was small and the range of exotherm was broad throughout the exotherm for pure AP. Under the same condition, when 1-5% of ZIF-67@ Mo (CO) prepared in example 1 is added into the main component AP of the solid propellant 6 Then, the peak temperature of the AP pyrolysis stage is respectively reduced from 420.4 ℃ to 313.9 ℃, 309.3 ℃, 305.7 ℃, 306.6 ℃ and 313.7 ℃, and is respectively reduced by 106.5 ℃, 111.1 ℃, 114.7 ℃, 113.8 ℃ and 106.7 ℃, and is obviously higher than the AP test result; in addition, the apparent decomposition heat of AP was increased from 976.42J/g to 2282.40J/g, 2144.02J/g, 2281.38J/g, 2053.26J/g and 2152.08J/g, and 1305.98J/g, 1167.6J/g, 1304.96J/g, 1076.84J/g and 1175.66J/g, respectively, and it was found that 1% to 5% of ZIF-67@ Mo (CO) prepared in example 1 was added as compared with pure AP in the pyrolysis stage 6 Then, the pyrolysis of AP showed a concentrated heat release, the peak temperature of AP pyrolysis was significantly reduced, and the heat released by the system was increased much more than that of pure AP, indicating that the ZIF-67@ Mo (CO) prepared in example 1 6 Has good combustion catalysis effect on AP thermal decomposition, and 3% of ZIF-67@ Mo (CO) prepared in example 1 is added 6 The catalytic effect on AP thermal decomposition is best. As can be seen from FIG. 5, under the same conditions, when 3% of the ZIF-67 embedded metal carbonyl composite burn rate catalyst prepared in examples 1 to 3 was added to the solid propellant main component AP, the peak temperatures in the AP pyrolysis stage were decreased from 420.4 ℃ to 305.7 ℃, 303.4 ℃ and 307.9 ℃ respectively, and decreased from 114.7 ℃, 117.0 ℃ and 112.5 ℃ respectively, and the apparent decomposition heat of AP was increased from 976.42J/g to 2281.38J/g and 2061.86J/g respectivelyJ/g, 2223.86J/g, 1304.96J/g, 1085.44J/g, 1247.44J/g; in addition, the DSC test is carried out by directly adding the metal carbonyl compound and pure AP, and the pure metal carbonyl compound does not show obvious catalytic effect on the AP; the addition of pure ZIF-67 to catalyze AP greatly reduces the peak temperature, but the exothermic amount is not ideal. After 3% of the ZIF-67 embedded carbonyl metal composite burning rate catalyst prepared in examples 1 to 3 was added, the peak temperature of AP was greatly reduced, and the centralized heat release phenomenon was exhibited in the pyrolysis stage, and the heat release was significantly increased, indicating that the ZIF-67 embedded carbonyl metal composite burning rate catalyst prepared in the present invention has a good combustion catalytic effect on the thermal decomposition of AP, wherein the ZIF-67@ Mo (CO) prepared in example 1 6 The catalytic effect on AP thermal decomposition is best. As can be seen from FIG. 6, under the same conditions, when 3% of ZIF-67/Mo (CO) prepared in comparative example 1 was added to the solid propellant major component AP 6 The peak temperature of AP pyrolysis stage is reduced from 420.4 ℃ to 305.2 ℃, and the apparent decomposition heat of AP is increased from 976.42J/g to 1483.09J/g. When 3% of ZIF-67% of that prepared in comparative example 2 was added to the solid propellant major component AP, mo (CO) 6 The peak temperature of the AP pyrolysis stage is reduced from 420.4 ℃ to 304.1 ℃, and the apparent decomposition heat of the AP is increased from 976.42J/g to 1956.98J/g. When 3% of ZIF-67 prepared in comparative example 3 was added to the main component AP of the solid propellant&Mo(CO) 6 The peak temperature of the AP pyrolysis stage is reduced from 420.4 ℃ to 304.6 ℃, and the apparent decomposition heat of the AP is increased from 976.42J/g to 1697.92J/g. While 3% of ZIF-67@ Mo (CO) prepared in example 1 was added to the main solid propellant component AP 6 The peak temperature of the AP pyrolysis stage was reduced from 420.4 ℃ to 305.7 ℃ and the apparent heat of decomposition of AP increased from 976.42J/g to 2281.38J/g. Comparing the catalytic effects, it can be found that although the composite materials of comparative examples 1 to 3 all have certain catalytic effects on the thermal decomposition of AP, the high-temperature decomposition peaks of the composite materials all move to a low-temperature region, and the peak temperatures are not greatly different, the catalytic heat release of the ZIF-67 embedded carbonyl metal composite combustion rate catalyst prepared in examples 1 to 3 on AP is far higher than that of the composite materials of comparative examples 1 to 3 on AP, which shows that the combustion catalytic performance of the composite materials is superior to that of the composite materials loaded with carbonyl metal, ultrasonically filled and ultrasonically filled on ZIF-67 Combustion catalysis Performance.
The resulting MoCo-N-C, crCo-N-C, WCo-N-C calcined ZIF-67 chimeric metal carbonyl composite burn rate catalysts prepared in examples 1-3 were further added to 3% of the solid propellant main component AP for catalytic testing, respectively, and compared with the ZIF-67 chimeric metal carbonyl composite burn rate catalysts prepared in examples 1-3, and the results are shown in fig. 7. As can be seen from FIG. 7, the peak temperature of MoCo-N-C was advanced from 305.7 ℃ to 288.1 ℃ compared to that before calcination, but at the same time the exotherm was reduced from 2281.38J/g to 1238.29J/g; compared with the CrCo-N-C before calcination, the peak temperature is advanced from 303.4 ℃ to 290.9 ℃, the heat release is reduced from 2061.86J/g to 1229.35J/g, and the catalytic effect is poor. WCo-N-C has two exothermic peaks when catalyzing AP compared with before calcination, the peak temperatures are 291.9 ℃ and 306.9 ℃, the exothermic quantity is reduced from 2223.86J/g to 2212.95J/g, and the catalytic effect is general. Compared with a plurality of catalysts, the ZIF-67 embedded carbonyl metal composite burning rate catalyst prepared by the invention has the advantages of good catalytic effect, simple preparation method, convenient amplification and good market application prospect.
Claims (4)
1. A ZIF-67 embedded carbonyl metal composite burning rate catalyst is characterized in that: adding a saturated solution of a metal carbonyl compound in the process of preparing ZIF-67 by stirring cobalt nitrate and 2-methylimidazole serving as raw materials and methanol serving as a solvent at room temperature, washing the generated purple precipitate with the solvent corresponding to the saturated solution of the methanol and the metal carbonyl compound, performing suction filtration, and drying to obtain the ZIF-67 embedded metal carbonyl composite burning rate catalyst; the metal carbonyl compound is any one of molybdenum hexacarbonyl, chromium hexacarbonyl and tungsten hexacarbonyl.
2. The ZIF-67 embedded metal carbonyl composite burn rate catalyst of claim 1, wherein: the molar ratio of metal atoms of the carbonyl metal compound in the ZIF-67 embedded carbonyl metal nano composite burning rate catalyst to Co atoms in the ZIF-67 is 1:3-1:4.
3. The ZIF-67 embedded metal carbonyl composite burn rate catalyst of claim 1, wherein: the particle size of the ZIF-67 embedded carbonyl metal nano composite burning rate catalyst is 400-500 nm, and the ZIF-67 structure is reserved.
4. The ZIF-67 embedded metal carbonyl composite burn rate catalyst of claim 1, wherein: the solvent corresponding to the saturated solution of chromium hexacarbonyl is trichloromethane, the solvent corresponding to the saturated solution of molybdenum hexacarbonyl is benzene, and the solvent corresponding to the saturated solution of tungsten hexacarbonyl is tetrahydrofuran.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3954527A (en) * | 1970-03-24 | 1976-05-04 | The United States Of America As Represented By The Secretary Of The Army | Solid propellant with iron-carbonyl containing polymer binder |
| WO2013091387A1 (en) * | 2011-12-20 | 2013-06-27 | 陕西坚瑞消防股份有限公司 | Metal-carbonyl-containing fire extinguishing composition |
| US9233883B1 (en) * | 2013-03-15 | 2016-01-12 | Cornerstone Research Group, Inc. | Polymer composite comprising metal based nanoparticles in a polymer matrix |
| US20170369387A1 (en) * | 2016-06-24 | 2017-12-28 | The Regents Of The University Of Michigan | Explosive microporous coordination polymers |
| CA3055359A1 (en) * | 2018-09-13 | 2020-03-13 | Acsynam Inc. | Hypergolic metal organic frameworks |
| CN112939707A (en) * | 2021-02-05 | 2021-06-11 | 西安近代化学研究所 | Aluminum-based energetic MOFs and preparation method thereof |
| CN112940273A (en) * | 2021-02-05 | 2021-06-11 | 西安近代化学研究所 | Graphene-based energetic MOFs and preparation method thereof |
| CN113548932A (en) * | 2021-07-27 | 2021-10-26 | 陕西师范大学 | Nano composite burning rate catalyst of copper metal complex filled with carbon nano tube |
| CN114768873A (en) * | 2022-04-15 | 2022-07-22 | 西北大学 | Application of Fe-based metal organic framework material as combustion catalyst |
| CN114890851A (en) * | 2022-05-26 | 2022-08-12 | 陕西师范大学 | Nano composite burning rate catalyst with carbon nano tube embedded transition metal compound |
| 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 |
-
2022
- 2022-12-12 CN CN202211595134.3A patent/CN115974631B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3954527A (en) * | 1970-03-24 | 1976-05-04 | The United States Of America As Represented By The Secretary Of The Army | Solid propellant with iron-carbonyl containing polymer binder |
| WO2013091387A1 (en) * | 2011-12-20 | 2013-06-27 | 陕西坚瑞消防股份有限公司 | Metal-carbonyl-containing fire extinguishing composition |
| US9233883B1 (en) * | 2013-03-15 | 2016-01-12 | Cornerstone Research Group, Inc. | Polymer composite comprising metal based nanoparticles in a polymer matrix |
| US20170369387A1 (en) * | 2016-06-24 | 2017-12-28 | The Regents Of The University Of Michigan | Explosive microporous coordination polymers |
| CA3055359A1 (en) * | 2018-09-13 | 2020-03-13 | Acsynam Inc. | Hypergolic metal organic frameworks |
| CN112939707A (en) * | 2021-02-05 | 2021-06-11 | 西安近代化学研究所 | Aluminum-based energetic MOFs and preparation method thereof |
| CN112940273A (en) * | 2021-02-05 | 2021-06-11 | 西安近代化学研究所 | Graphene-based energetic MOFs and preparation method thereof |
| CN113548932A (en) * | 2021-07-27 | 2021-10-26 | 陕西师范大学 | Nano composite burning rate catalyst of copper metal complex filled with carbon nano tube |
| CN114768873A (en) * | 2022-04-15 | 2022-07-22 | 西北大学 | Application of Fe-based metal organic framework material as combustion catalyst |
| 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 |
| CN114890851A (en) * | 2022-05-26 | 2022-08-12 | 陕西师范大学 | Nano composite burning rate catalyst with carbon nano tube embedded transition metal compound |
Non-Patent Citations (3)
| Title |
|---|
| WANG S;YE B Y;AN C W;ET AL: "Synergistic catalysis of ZIF-67@CNTOH in thermal decomposition of ammonium perchlorate", JOURNAL OF MATERIALS SCIENCE, vol. 55, no. 11, pages 4646 - 4655, XP036988981, DOI: 10.1007/s10853-019-04321-x * |
| XU R Z;YANG L F;FANG H C;ET AL: "Copper Complexes in Carbon Nanotubes as Catalysts for Thermal Decomposition of Energetic Oxidizers", ACS APPLIED NANO MATERIALS, vol. 5, no. 10, 30 September 2022 (2022-09-30), pages 14942 - 14953 * |
| 李海涛: "纳米ZIF-67、ZnO及其复合材料的合成、结构调控和促进AP热分解的性能研究", 中国博士学位论文全文数据库•工程科技Ⅱ辑, no. 2019, pages 1 - 139 * |
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