CN117384390A - Preparation method of high-stability high-energy EMOFs material - Google Patents
Preparation method of high-stability high-energy EMOFs material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 157
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
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- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- HYKRXUIBPGRUFN-UHFFFAOYSA-N bis(1,2,4-triazol-4-yl)diazene Chemical compound C1=NN=CN1N=NN1C=NN=C1 HYKRXUIBPGRUFN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- 238000005728 strengthening Methods 0.000 claims description 3
- -1 salt hydrates Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 description 53
- QJTIRVUEVSKJTK-UHFFFAOYSA-N 5-nitro-1,2-dihydro-1,2,4-triazol-3-one Chemical compound [O-][N+](=O)C1=NC(=O)NN1 QJTIRVUEVSKJTK-UHFFFAOYSA-N 0.000 description 38
- 238000012360 testing method Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 17
- 230000035945 sensitivity Effects 0.000 description 16
- 230000001105 regulatory effect Effects 0.000 description 13
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- 239000002360 explosive Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 238000000982 solution X-ray diffraction Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000004880 explosion Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Abstract
The invention relates to the technical field of energetic materials, and particularly discloses a preparation method of a high-stability high-energy EMOFs material, which comprises the following steps: s01: respectively adding the raw materials into a solvent, heating, stirring until the raw materials are completely dissolved, and filtering to obtain raw material solutions respectively; the raw materials comprise metal ion salts, nitrogen-rich azole ligands and high-energy molecule regulators; the raw material solution comprises a metal ion salt solution, a nitrogen-rich azole ligand solution and a high-energy molecule regulator solution; s02: mixing the raw material solutions according to a mixing sequence, stirring, dripping an enhanced acid solution for the first time, stirring at constant temperature, and filtering to obtain a transparent mixed solution; s03: transferring the clear and transparent mixed solution into a reaction device, dripping an enhanced acid solution for the second time, sealing the reaction device in a constant-temperature oven, standing, and obtaining the precipitated transparent crystal which is the high-stability high-energy EMOFs material.
Description
Technical Field
The invention relates to the technical field of energetic materials, in particular to a preparation method of a high-stability high-energy EMOFs material.
Background
The Energetic Metal Organic Frameworks (EMOFs) material is a coordination compound which is formed by self-assembling molecules through the coordination interaction drive of polyazole energetic organic ligands and metal ions and has different dimensionalities and space structures. As an important component of energetic materials, EMOFs materials are receiving widespread attention by virtue of stable geometric topologies, programmable energetic ligands, tunable detonation properties and safety. From the chemical structure of the EMOFs material, the EMOFs material mainly comprises single coordination metal ions and single organic energetic ligands, and the preparation of the novel EMOFs material by replacing different single coordination metal ions or single organic energetic ligands is the most main method for regulating the physicochemical properties of the novel EMOFs material. However, for most EMOFs materials, changing the coordination metal ion or the organic energetic ligand cannot ensure that an EMOFs material with a brand new structure and performance can be synthesized, and the difficulty of synthesizing a new EMOFs material with application potential is large and uncontrollable, so how to adjust the skeleton structure of the EMOFs material to realize the improvement of the performance and application is a current urgent problem to be solved.
Disclosure of Invention
Aiming at the problems, the invention aims to provide the preparation method of the high-stability high-energy EMOFs material, which is simple to operate, safe and efficient in preparation of the high-stability high-energy EMOFs material, and can effectively improve the energy characteristics and stability of the EMOFs material while maintaining the integrity of the skeleton structure of the original EMOFs material.
The technical scheme adopted by the invention is as follows: a preparation method of a high-stability high-energy EMOFs material comprises the following steps:
s01: respectively adding the raw materials into a solvent, heating, stirring until the raw materials are completely dissolved, and filtering to obtain raw material solutions respectively;
the raw materials comprise metal ion salts, nitrogen-rich azole ligands and high-energy molecule regulators;
the raw material solution comprises a metal ion salt solution, a nitrogen-rich azole ligand solution and a high-energy molecule regulator solution;
s02: mixing the raw material solutions according to a mixing sequence, stirring, dripping an enhanced acid solution for the first time, stirring at constant temperature, and filtering to obtain a clear and transparent mixed solution;
s03: transferring the clear and transparent mixed solution into a reaction device, dripping an enhanced acid solution for the second time, sealing the reaction device in a constant-temperature oven, standing, and obtaining the precipitated transparent crystal which is the high-stability high-energy EMOFs material.
Preferably, the metal ion salt comprises Cu (NO 3 ) 2 、Cu(BF 4 ) 2 、CuSO 4 、Co(NO 3 ) 2 、Co(BF 4 ) 2 、CoCl 2 、Zn(NO 3 ) 2 、Zn(BF 4 ) 2 、ZnSO 4 、Fe(NO 3 ) 2 、FeSO 4 、FeCl 2 、Ni(NO 3 ) 2 、NiCl 2 And one of its corresponding metal ion salt hydrates;
the concentration of the metal ion salt solution is more than or equal to 1.5 mg.mL -1 。
Preferably, the azole-rich ligand is 4,4' -azo-1, 2, 4-triazole.
Preferably, the high-energy molecular regulator comprises one of 5,5 '-bitetrazole-1, 1' -dioxyhydroxylammonium salt and 3-nitro-1, 2, 4-triazole-5-ketone.
Preferably, the solvent is one of deionized water, methanol, ethanol, acetonitrile, acetone, ethyl acetate and dichloromethane.
Preferably, in the step S02, the mixing sequence is that firstly, a metal ion salt solution and a nitrogen-rich azole ligand solution are mixed, and then a high-energy molecule regulator solution is added; stirring for 1-3 h at 30-70 ℃, dripping the reinforcing acid solution into the mixture for the first time, and stirring for 0.5-2 h at constant temperature;
the standing condition in the step S03 is that the standing is carried out for 7 to 14 days at the temperature of 20 to 60 ℃.
Preferably, the molar ratio of the metal ion salt solution to the nitrogen-rich azole ligand solution is 5:1-1:5;
the high-energy molecular regulator solution is less than or equal to 40wt% of the total solution.
Preferably, the strong acid solution is 38% concentrated HCl, 98% concentrated H 2 SO 4 And 68% concentrated HNO 3 One of them.
Preferably, the first drop of strengthening acid solution is 1% -10% of the total volume of the solution.
Preferably, the second drop of the strengthening acid solution is 1 to 10 drops.
The beneficial effects of the technical scheme are that:
(1) The invention uses the high-energy explosive in the adjustment of the physical and chemical properties of the EMOFs material, has simple operation, safety and high efficiency, and realizes the modification of the chemical structure and the adjustment of the spatial structure of the EMOFs material by means of certain coordination interaction between the high-energy explosive and the metal central atom of the EMOFs material, thereby realizing the adjustment of the physical and chemical properties of the EMOFs material.
(2) The high-stability high-energy EMOFs material with the adjusted physical and chemical properties can keep the integrity of the skeleton structure of the original EMOFs material, and can effectively improve the energy characteristics and stability of the EMOFs material.
(3) The invention adopts high-energy explosive TKX-50 and NTO as high-energy molecular regulator, when the dosage is inconsistent, the comparison difference of the physicochemical properties of the obtained EMOFs material is obvious.
(4) The high-stability high-energy EMOFs material prepared by adopting the high-energy explosive TKX-50 and NTO as high-energy molecular regulators has the potential of being used as a heat-resistant insensitive explosive.
Drawings
FIG. 1 is a graph of the coordination environment of an EMOF-1 material of comparative example one obtained by X-ray single crystal diffraction test (SXRD);
FIG. 2 is a Scanning Electron Microscope (SEM) image of an EMOF-1 material of comparative example one;
FIG. 3 is a Scanning Electron Microscope (SEM) image of an EMOF-1@5wt% TKX-50 material in example one;
FIG. 4 is a Scanning Electron Microscope (SEM) image of an EMOF-1@10wt% TKX-50 material in example two;
FIG. 5 is an infrared spectrum (FT-IR) of a high stability, high energy EMOFs material in comparative example one, example one and example two;
FIG. 6 is an X-ray powder diffraction (PXRD) diagram of a high stability, high energy EMOFs material in comparative example one, example one and example two;
FIG. 7 is a Differential Scanning Calorimeter (DSC) plot of a comparative example one, and example two high stability high energy EMOFs materials;
FIG. 8 is a 3D crystal packing plot obtained by SXRD of the EMOF-2 material of comparative example two;
FIG. 9 is a Scanning Electron Microscope (SEM) image of an EMOF-2 material of comparative example two;
FIG. 10 is a Scanning Electron Microscope (SEM) image of an EMOF-2@5wt% NTO material in example three;
FIG. 11 is a Scanning Electron Microscope (SEM) image of an EMOF-2@10wt% NTO material in example four;
FIG. 12 is an infrared spectrum (FT-IR) of a high stability, high energy EMOFs material in comparative example two, example three, and example four;
FIG. 13 is an X-ray powder diffraction (PXRD) pattern of the high stability, high energy EMOFs materials of comparative example two, example three and example four;
fig. 14 is a Differential Scanning Calorimetric (DSC) plot of high stability, high energy EMOFs materials in comparative example two, example three, and example four.
Detailed Description
The following detailed description of the embodiments of the present application is provided in further detail, and it is apparent that the described embodiments are only some, but not all, examples of the present application. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
The terms first, second, and the like in the description and in the claims, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments described herein may be implemented in other sequences than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements that are expressly listed or inherent to such process, method, article, or apparatus.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
Raw materials and equipment:
(1) Unless otherwise specified, the materials and equipment employed are commercially available or are conventional in the art.
(2) Synthesis of ATRZ used the energetic material, 2015,23 (5): 420-423 according to the synthesis process modification [ J ]. The energetic material of the literature "Xue Linjun, shang Zhan, bi Yangang, et al, 4 '-azo-1, 2, 4-triazole", the chemical structural formula of said ATRZ (4, 4' -azo-1, 2, 4-triazole) is as follows:
(3) Synthesis of TKX-50 used was carried out according to the literature "Zhu Zhoushuo, jiang Zhenming, wang Pengcheng, et al, synthesis of 5,5 '-bitetrazole-1, 1' -dioxydihydroxyammonium and its properties [ J ]. Energetic materials, 2014,22 (3): 332-336". The chemical formula of TKX-50 (5, 5 '-bitetrazole-1, 1' -dioxydihydroxyammonium) is as follows:
(4) The synthesis of NTO used is according to the literature Liu Xin, li Yana, chang Pei, etc. NTO and its derivatives are synthesized and applied as research progress [ J ]. Chemical propellants and polymeric materials, 2021,19 (2): 18-23 ". The chemical structural formula of NTO (3-nitro-1, 2, 4-triazol-5-one) is as follows:
(5) SEM test: a scanning electron microscope model S4800 manufactured by Hitachi Corp.
(6) FT-IR test: an infrared spectrometer of Nicolet Magna IR 560 type manufactured by Bruker corporation was used.
(7) PXRD test: a Bruker D2 Advance type diffractometer manufactured by Bruker corporation was used.
(8) SXRD test: a Rigaku RAXIS IP type diffractometer manufactured by Bruker company was used.
(9) DSC test: a differential scanning calorimeter of the type DSC-209 produced by Netzsch was used.
(10) True density testing: a full-automatic true density analyzer manufactured by Micromeritics company, accoumycII 1345 was used.
(11) Burst heat test: a Parr 6772 full-automatic oxygen bomb calorimeter manufactured by Parr company was used.
(12) Impact sensitivity test: BFH-10 crash sensitivity apparatus manufactured by Idea Science was used.
(13) Friction sensitivity test: an FSKM-10 BAM friction sensor manufactured by Idea Science was used.
Comparative example one
The EMOF-1 material was prepared in this example as follows:
(1) Cu (NO) 3 ) 2 ·3H 2 O (242 mg,1 mmol) and ATRZ (164 mg,1 mmol) were added separately toHeating, stirring and filtering 10mL deionized water to obtain clear and transparent Cu (NO) 3 ) 2 Solutions and ATRZ solutions;
(2) Cu (NO) 3 ) 2 Slowly dripping the solution into a three-mouth bottle filled with ATRZ solution, stirring and reacting for 1h under the heating of a water bath at 55 ℃, and then dripping 0.5ml of 68% concentrated HNO into the three-mouth bottle 3 The solution is kept warm for reaction for 0.5h, and after the reaction is finished, the solution is filtered to obtain clear and transparent mixed solution;
(3) The above-obtained mixed solution was transferred to a glass vial, and 3 drops of 68% concentrated HNO were added thereto again 3 And (3) standing the solution for 10 days at room temperature, wherein the blue transparent crystals separated out from the glass bottle are the EMOF-1 material with unregulated physical and chemical properties.
SXRD testing of EMOF-1 material, as shown in FIG. 1, is performed on a coordinated environmental pattern obtained by X-ray single crystal diffraction testing (SXRD) of EMOF-1 material, and the result shows that the EMOF-1 is a material prepared by Cu 2+ As coordination center ion, ATRZ is organic ligand, NO 3 - An energetic metal-organic framework material which is a counter ion. FIG. 2 is a Scanning Electron Microscope (SEM) image of the EMOF-1 material of example 1.
Physical and chemical property characterization of EMOF-1 material shows that its density is 1.68 g.cm -3 The heat of combustion and explosion is 4388 kJ.kg -1 Impact sensitivity was 16J, friction sensitivity was 112N, thermal decomposition temperature (heating rate was 15 ℃ C. Min -1 As shown in fig. 7) is 312.48 ℃, and the comprehensive performance is excellent.
Example 1
EMOF-1@5wt% TKX-50 material was prepared as follows:
(1) Cu (NO) 3 ) 2 ·3H 2 O (242 mg,1 mmol), ATRZ (164 mg,1 mmol) and TKX-50 (21.4 mg,0.09 mmol) were added to 10mL of deionized water, respectively, and the mixture was heated, stirred and filtered to give clear and transparent Cu (NO) 3 ) 2 Solutions, ATRZ solutions and TKX-50 solutions;
(2) Cu (NO) 3 ) 2 Slowly dripping the solution into a three-mouth bottle filled with ATRZ solution, stirring and reacting for 0.5h under the heating of 55 ℃ water bath, and continuingDropwise adding TKX-50 solution, and reacting for 1h after the completion of dropwise adding;
(3) 0.5mL of 68% concentrated HNO was added dropwise to the three-necked flask again 3 The solution is kept warm for reaction for 0.5h, and after the reaction is finished, the solution is filtered to obtain clear and transparent mixed solution;
(4) Transferring the obtained mixed solution into a small glass bottle, adding 3 drops of 68% concentrated HNO3 solution into the small glass bottle again, covering a bottle cap, standing the glass bottle in a constant temperature oven at 40 ℃ for 14 days, and obtaining the transparent crystals separated out from the glass bottle, namely the high-stability high-energy EMOFs material, namely the EMOF-1@5wt% TKX-50 material with the regulated physicochemical properties.
FT-IR tests were performed on the physicochemical modified EMOF-1@5wt% TKX-50 material, as shown in FIG. 5, and the results indicate that the EMOF-1@5wt% TKX-50 material is a complex of EMOF-1 and TKX-50, and that the red-blue shift of part of the infrared peak and the generation of a new peak may be related to the coordination interaction of TKX-50.
As shown in FIG. 6, the result shows that the EMOF-1@5wt% TKX-50 material with the adjusted physical and chemical properties is consistent with the EMOF-1 material with the adjusted physical and chemical properties, and obvious strong diffraction peaks exist, which indicates that the EMOF-1@5wt% TKX-50 material with the adjusted physical and chemical properties still maintains the basic skeleton structure of the original material.
SEM test is carried out on the EMOF-1@5wt% TKX-50 material after the physical and chemical properties are regulated, as shown in figure 3, the result shows that the EMOF-1@5wt% TKX-50 material after the physical and chemical properties are basically consistent with the EMOF-1 material before the physical and chemical properties are regulated, and the EMOF-1@5wt% TKX-50 material after the physical and chemical properties are all regular blocky crystals, so that the integral crystal morphology of the EMOF-1 material is not destroyed by the introduction of TKX-50 with the mass fraction of 5%.
The corresponding physical and chemical property characterization of the EMOF-1@5wt%TKX-50 material shows that the density is 1.72 g.cm < -3 >, the heat of ignition is 4790 kJ.kg < -1 >, the impact sensitivity is 14J, the friction sensitivity is 144N, the thermal decomposition temperature (the temperature rising rate is 15 ℃ C. Min < -1 >. As shown in figure 7) is 315.90 ℃, and the physical and chemical properties are obviously changed compared with those of the EMOF-1 material.
Example two
In this example, TKX-50 in step (1) was replaced by 45.1mg (0.19 mmol) from 21.4mg (0.09 mmol), and the product was EMOF-1@10wt% TKX-50 material as in example one.
FT-IR tests were performed on the physicochemical modified EMOF-1@10wt% TKX-50 material, as shown in FIG. 5, and the results show that the EMOF-1@10wt% TKX-50 material is a complex of EMOF-1 and TKX-50, and that the red-blue shift of part of infrared peaks and the generation of new peaks may be related to coordination interactions of TKX-50.
As shown in FIG. 6, the result shows that the EMOF-1@10wt% TKX-50 material with the adjusted physical and chemical properties is consistent with the EMOF-1 material with the adjusted physical and chemical properties, and obvious strong diffraction peaks exist, which indicates that the EMOF-1@10wt% TKX-50 material with the adjusted physical and chemical properties still maintains the basic skeleton structure of the original material.
SEM test of the EMOF-1@10wt% TKX-50 material after physical and chemical property adjustment is shown in FIG. 4, and the result shows that the EMOF-1@10wt% TKX-50 material after physical and chemical property adjustment is basically consistent with the EMOF-1 material before physical and chemical property adjustment, and the EMOF-1@10wt% TKX-50 material after physical and chemical property adjustment is regular blocky crystals, so that the integral crystal morphology of the EMOF-1 material is not destroyed due to the introduction of the TKX-50 with the mass fraction of 10%.
FIG. 5 is an infrared spectrum (FT-IR) of the high-stability high-energy EMOFs material in the first comparative example and the second example, and FIG. 6 is an X-ray powder diffraction (PXRD) of the high-stability high-energy EMOFs material in the first comparative example and the second example, and the test result shows that the partial diffraction peaks of the EMOF-1@10wt% TKX-50 material and the EMOF-1@5wt% TKX-50 material are inconsistent, which can be attributed to the variation of the TKX-50 content.
The EMOF-1@10wt% TKX-50 material is subjected to corresponding physical and chemical property characterization, and the result shows that the density is 1.77 g.cm -3 The heat of combustion and explosion is 5226 kJ.kg -1 Impact sensitivity of 15J, friction sensitivity of 216N, thermal decomposition temperature (heating rate of 15 ℃ C. Min -1 When the temperature is 317.26 ℃, the physical and chemical properties are obviously changed compared with those of the EMOF-1 material and the EMOF-1@5wt% TKX-50 material.
The results of the first comparative example and the first and the second examples show that the molecular type high-nitrogen energetic compound and the ionic type high-nitrogen energetic salt are important components of the high-energy explosive based on the structural characteristics and performance advantages of the high-energy explosive, the molecular structure of the molecular type high-nitrogen energetic compound contains a large number of N-N bonds and C-N bonds, the high positive formation enthalpy is achieved, and the high nitrogen and low hydrocarbon content in the molecule enable the molecular type high-nitrogen energetic compound to easily reach oxygen balance. The ionic high nitrogen energetic salt using the high nitrogen heterocyclic energetic anion as the core skeleton structure is widely used in the energetic field because of having lower vapor pressure and higher density than the high nitrogen energetic compound. The molecular regulator is introduced into the EMOFs material, and has great significance for regulating the physical and chemical properties of the EMOFs material. The method successfully realizes the adjustment of the energy characteristics and stability of the EMOF-1 material, and simultaneously ensures that the framework structure of the EMOF-1 material is kept complete.
Comparative example two
In this example, cu (NO) in step (1) 3 ) 2 ·3H 2 O is replaced by Co (BF 4 ) 2 (233 mg,1 mmol) and the rest were the same as in example 1. The obtained pale red transparent crystal is EMOF-2 material with unregulated physical and chemical properties.
SXRD testing of EMOF-2 material, as shown in FIG. 8, shows a 3D crystal stacking diagram, which shows that EMOF-2 is a material prepared from Co 2+ ATRZ is an organic ligand, BF 4 - An energetic metal-organic framework material which is a counter ion. FIG. 9 is a Scanning Electron Microscope (SEM) image of an EMOF-2 material of comparative example two.
Physical and chemical property characterization of EMOF-2 material shows that its density is 1.64g cm -3 The heat of combustion and explosion is 4223 kJ.kg -1 Impact sensitivity was 15J, friction sensitivity was 120N, thermal decomposition temperature (heating rate was 15℃min -1 As shown in fig. 14) is 319.09 ℃, and the comprehensive performance is excellent.
Example III
In this example, cu (NO) in step (1) 3 ) 2 ·3H 2 O is replaced by Co (BF 4 ) 2 (233 mg,1 mmol) TKX-50 was replaced with NTO (20.9 mg,0.16 mmol), and the product was EM as in example oneOF-2@5wt% NTO material.
FT-IR tests were performed on the EMOF-2@5wt% NTO material with the physical and chemical properties adjusted, as shown in FIG. 12, and the results show that the EMOF-2@5wt% NTO material is a compound of EMOF-2 and NTO, and the red-blue shift of part of infrared peaks and the generation of new peaks are possibly related to the coordination interaction of NTO.
The result of PXRD test on the EMOF-2@5wt% NTO material after the physical and chemical properties are regulated shows that the EMOF-2@5wt% NTO material after the physical and chemical properties are consistent with the EMOF-2 material before the physical and chemical properties are regulated, and obvious strong diffraction peaks exist, so that the basic skeleton structure of the original material is still maintained by the EMOF-2@5wt% NTO material after the physical and chemical properties are regulated.
SEM test of the EMOF-2@5wt% NTO material after physical and chemical property adjustment is shown in FIG. 10, and the result shows that the EMOF-2@5wt% NTO material after physical and chemical property adjustment is basically consistent with the EMOF-2 material before physical and chemical property adjustment, and the EMOF-2 material is a crystal with a larger lamellar, which shows that the integral crystal morphology of the EMOF-2 material is not destroyed by introducing the NTO with the mass fraction of 5%.
The corresponding physical and chemical property characterization of the EMOF-2@5wt% NTO material shows that the density is 1.67 g.cm -3 The heat of combustion and explosion is 4564 kJ.kg -1 Impact sensitivity of 15J, friction sensitivity of 252N, thermal decomposition temperature (heating rate of 15 ℃ C. Min -1 As in fig. 14) is 333.01 ℃, the physical and chemical properties are obviously changed compared with those of the EMOF-2 material.
Example IV
In this example, cu (NO) in step (1) 3 ) 2 ·3H 2 O is replaced by Co (BF 4 ) 2 (233 mg,1 mmol) TKX-50 was replaced with NTO (44.1 mg,0.33 mmol) and the product was EMOF-2@10wt% NTO material as in example two.
FT-IR tests were performed on the EMOF-2@10wt% NTO material with the physical and chemical properties adjusted, as shown in FIG. 12, and the results show that the EMOF-2@10wt% NTO material is a compound of EMOF-2 and NTO, and the red-blue shift of part of infrared peaks and the generation of new peaks are possibly related to the coordination interaction of NTO.
As shown in FIG. 13, the result shows that the EMOF-2@10wt% NTO material after the physical and chemical properties are consistent with the EMOF-2 material before the physical and chemical properties are regulated, and obvious strong diffraction peaks exist, which indicates that the EMOF-2@10wt% NTO material after the physical and chemical properties are regulated still maintains the basic skeleton structure of the original material.
SEM test is carried out on the EMOF-2@10wt% NTO material after the physical and chemical properties are regulated, as shown in FIG. 11, the result shows that the EMOF-2@10wt% NTO material after the physical and chemical properties are basically consistent with the EMOF-2 material before the physical and chemical properties are regulated, and the EMOF-2 material is a crystal with a larger lamellar, which shows that the integral crystal morphology of the EMOF-2 material is not destroyed by the introduction of the NTO with the mass fraction of 10%.
FIG. 12 is an infrared spectrum (FT-IR) of the high-stability high-energy EMOFs material in the second and third examples and fourth example, and FIG. 13 is an X-ray powder diffraction (PXRD) of the high-stability high-energy EMOFs material in the second and third examples and fourth example, and the test result shows that the partial diffraction peak intensities of the EMOF-2@10wt% NTO material and the EMOF-2@5wt% NTO material are inconsistent, which can be attributed to the variation of NTO content.
The corresponding physical and chemical property characterization of the EMOF-2@10wt% NTO material shows that the density is 1.67 g.cm -3 The heat of combustion and explosion is 5066 kJ.kg -1 Impact sensitivity was 16J, friction sensitivity was 288N, thermal decomposition temperature (heating rate was 15 ℃ C. Min -1 When the temperature is as shown in figure 14), the physical and chemical properties are obviously changed compared with those of the EMOF-2 material and the EMOF-2@5wt% NTO material at 336.32 ℃.
The above results indicate that the method described in this example successfully achieved the adjustment of the energy characteristics and stability of the EMOF-2 material while leaving its framework structure intact.
From the above comparative and example data, the high-stability high-energy EMOFs material has potential as a heat-resistant insensitive explosive according to the analysis of the test results of density, heat of ignition, impact sensitivity, friction height and thermal decomposition temperature,
the invention uses TKX-50 and NTO as high-energy molecule regulator, realizes the physical and chemical property regulation of the EMOFs material by an in-situ synthesis method, has simple operation, safety and high efficiency, and the obtained EMOFs material with the physical and chemical property regulated can not only keep the integrity of the skeleton structure of the original EMOFs material, but also effectively improve the energy characteristic and stability of the EMOFs material. Provides a brand new research thought for the modification of the metal organic framework energetic material, and has wide application prospect.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (10)
1. The preparation method of the high-stability high-energy EMOFs material is characterized by comprising the following steps of:
s01: respectively adding the raw materials into a solvent, heating, stirring until the raw materials are completely dissolved, and filtering to obtain raw material solutions respectively;
the raw materials comprise metal ion salts, nitrogen-rich azole ligands and high-energy molecule regulators;
the raw material solution comprises a metal ion salt solution, a nitrogen-rich azole ligand solution and a high-energy molecule regulator solution;
s02: mixing the raw material solutions according to a mixing sequence, stirring, dripping an enhanced acid solution for the first time, stirring at constant temperature, and filtering to obtain a clear and transparent mixed solution;
s03: transferring the clear and transparent mixed solution into a reaction device, dripping an enhanced acid solution for the second time, sealing the reaction device in a constant-temperature oven, standing, and obtaining the precipitated transparent crystal which is the high-stability high-energy EMOFs material.
2. The method for preparing the high-stability high-energy EMOFs material according to claim 1, wherein the method comprises the steps of,the metal ion salt comprises Cu (NO) 3 ) 2 、Cu(BF 4 ) 2 、CuSO 4 、Co(NO 3 ) 2 、Co(BF 4 ) 2 、CoCl 2 、Zn(NO 3 ) 2 、Zn(BF 4 ) 2 、ZnSO 4 、Fe(NO 3 ) 2 、FeSO 4 、FeCl 2 、Ni(NO 3 ) 2 、NiCl 2 And one of its corresponding metal ion salt hydrates;
the concentration of the metal ion salt solution is more than or equal to 1.5 mg.mL -1 。
3. The method for preparing the high-stability and high-energy EMOFs material according to claim 1, wherein the azole-rich ligand is 4,4' -azo-1, 2, 4-triazole.
4. The method for preparing the high-stability high-energy EMOFs material according to claim 1, wherein the high-energy molecular regulator comprises one of 5,5 '-bitetrazole-1, 1' -dioxyhydroxylammonium salt and 3-nitro-1, 2, 4-triazole-5-ketone.
5. The method for preparing the high-stability and high-energy EMOFs material according to claim 1, wherein the solvent is one of deionized water, methanol, ethanol, acetonitrile, acetone, ethyl acetate and dichloromethane.
6. The method for preparing the high-stability high-energy EMOFs material according to claim 1, wherein in the step S02, the mixing sequence is that a metal ion salt solution and a nitrogen-rich azole ligand solution are mixed first, and then a high-energy molecule regulator solution is added; stirring for 1-3 h at 30-70 ℃, dripping the reinforcing acid solution into the mixture for the first time, and stirring for 0.5-2 h at constant temperature;
the standing condition in the step S03 is that the standing is carried out for 7 to 14 days at the temperature of 20 to 60 ℃.
7. The preparation method of the high-stability high-energy EMOFs material according to claim 6, wherein the molar ratio of the metal ion salt solution to the azole-rich ligand solution is 5:1-1:5;
the high-energy molecular regulator solution is less than or equal to 40wt% of the total solution.
8. The method for preparing the high-stability high-energy EMOFs material according to claim 1, wherein the strong acid solution is 38% concentrated HCl and 98% concentrated H 2 SO 4 And 68% concentrated HNO 3 One of them.
9. The method for preparing the high-stability and high-energy EMOFs material according to claim 1, wherein the amount of the first drop of the strengthening acid solution is 1% -10% of the total volume of the solution.
10. The method for preparing the high-stability and high-energy EMOFs material according to claim 1, wherein the second drop of reinforcing acid solution is 1-10 drops.
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