阅读说明：本技术 一种含硝基富氮杂环阴离子的二维含能CMOFs材料及其制备方法 (Two-dimensional energy-containing CMOFs material containing nitro nitrogen-rich heterocyclic anions and preparation method thereof ) 是由 李生华 彭盼盼 庞思平 丁宁 李亚琼 于 2020-12-02 设计创作，主要内容包括：本发明涉及一种含硝基富氮杂环阴离子的二维含能CMOFs材料及其制备方法,属于含能材料领域。所述材料由配位金属阳离子、中性有机配体和骨架平衡阴离子组成,其中,所述配位金属阳离子为过渡金属铜离子、钴离子、锌离子或铁离子,所述中性有机配体为ATRZ,所述骨架平衡阴离子为带有1～3个硝基基团的富氮杂环含能阴离子；通过中性含能有机配体ATRZ、富氮杂环阴离子盐和无机金属盐混合反应后得到。所述含能CMOFs材料具有更高的密度、更高的氮氧含量和更高的爆轰热。(The invention relates to a two-dimensional energy-containing CMOFs material containing nitro nitrogen-rich heterocyclic anions and a preparation method thereof, belonging to the field of energy-containing materials. The material consists of coordination metal cations, neutral organic ligands and framework balancing anions, wherein the coordination metal cations are transition metal copper ions, cobalt ions, zinc ions or iron ions, the neutral organic ligands are ATRZ, and the framework balancing anions are nitrogen-rich heterocyclic energetic anions with 1-3 nitro groups; the catalyst is obtained by mixing and reacting neutral energy-containing organic ligand ATRZ, nitrogen-rich heterocyclic anion salt and inorganic metal salt. The energetic CMOFs materials have higher densities, higher nitrogen oxygen contents, and higher detonation heats.)

1. A two-dimensional energy-containing CMOFs material containing nitro nitrogen-rich heterocyclic anions is characterized in that: the material consists of coordination metal cations, neutral organic ligands and framework balancing anions, wherein the coordination metal cations are transition metal copper ions, cobalt ions, zinc ions or iron ions, the neutral organic ligands are ATRZ, and the framework balancing anions are nitrogen-rich heterocyclic energetic anions containing 1-3 nitro groups.

2. The two-dimensional energetic CMOFs material containing the nitro nitrogen-rich heterocyclic anion as claimed in claim 1, wherein: when the metal cation is copper ion, the skeleton balancing anion is NTT^-、DNT^-、TNP^-、NTTO^-、DNTO^-And TNPO^-One ofMore than one seed; when the metal cation is cobalt ion, the backbone counter anion is NTT^-And/or DNT^-(ii) a When the metal cation is zinc ion or iron ion, the skeleton balancing anion is DNT^-。

3. A method for preparing the two-dimensional energetic CMOFs material containing the nitro nitrogen-rich heterocyclic anion according to claim 1, which is characterized in that: the method comprises the following steps:

adding a nitrogen-rich heterocyclic anionic salt solution containing 1-3 nitro groups and an inorganic metal salt solution into an ATRZ aqueous solution, uniformly mixing, and stirring at 25-30 ℃ for 0.5-2 h; after stirring, filtering, collecting filtrate, standing at room temperature until crystals are completely separated out, filtering out the crystals, washing with water, and drying in vacuum to obtain the two-dimensional energy-containing CMOFs material containing the nitro nitrogen-rich heterocyclic anions;

wherein the molar ratio of ATRZ, the nitrogen-rich heterocyclic anion salt and the inorganic metal salt is 3:0.2: 3-3: 4: 3;

the inorganic metal salt is copper salt, cobalt salt, zinc salt or ferrous salt.

4. The preparation method of the two-dimensional energy-containing CMOFs material containing the nitro nitrogen-rich heterocyclic anion, which is disclosed by claim 3, is characterized in that: when the inorganic metal salt is a copper salt, the nitrogen-rich heterocyclic anion salt is more than one of NTTA, DNTA, TNPA, NTTOA, DNTOA and TNPOA;

when the inorganic metal salt is a cobalt salt, the nitrogen-rich heterocyclic anion salt containing the nitro is NTTA and/or DNTA;

when the inorganic metal salt is cobalt salt or ferrous salt, the nitrogen-rich heterocyclic anion salt containing the nitro is DNTA.

5. The preparation method of the two-dimensional energy-containing CMOFs material containing the nitro nitrogen-rich heterocyclic anion, which is disclosed by claim 3, is characterized in that: during mixing, ATRZ aqueous solution, nitrogen-rich heterocyclic anion salt solution containing nitro and inorganic metal salt solution are added in sequence.

6. The preparation method of the two-dimensional energy-containing CMOFs material containing the nitro nitrogen-rich heterocyclic anion, which is disclosed by claim 3, is characterized in that: the molar ratio of ATRZ, the nitrogen-rich heterocyclic anion salt and the inorganic metal salt is 3:1.5: 3-3: 3: 3.

7. The preparation method of the two-dimensional energy-containing CMOFs material containing the nitro nitrogen-rich heterocyclic anion, which is disclosed by claim 3, is characterized in that: the solution molar concentration of ATRZ, the nitrogen-rich heterocyclic anion salt and the inorganic metal salt is 0.1-0.4 mol/L.

8. The preparation method of the two-dimensional energy-containing CMOFs material containing the nitro nitrogen-rich heterocyclic anion, which is disclosed by claim 3, is characterized in that: the standing time is 3-7 days.

9. The preparation method of the two-dimensional energy-containing CMOFs material containing the nitro nitrogen-rich heterocyclic anion, which is disclosed by claim 3, is characterized in that: the vacuum drying temperature is 50-80 ℃, and the drying time is 5-7 h.

10. The preparation method of the two-dimensional energy-containing CMOFs material containing the nitro nitrogen-rich heterocyclic anion, which is disclosed by claim 3, is characterized in that: the copper salt is Cu (BF)₄)₂·6H₂O、Cu(NO₃)₂·3H₂O and CuSO₄·5H₂O or more; the cobalt salt is Co (NO)₃)₂·5H₂O and/or Co (BF)₄)₂·5H₂O; the zinc salt is Zn (ClO)₄)₂·6H₂O and/or Zn (NO)₃)₂·6H₂O; the ferrous salt is FeSO₄·7H₂O and/or Fe (NO)₃)₂。

Technical Field

The invention relates to a two-dimensional energy-containing CMOFs material containing nitro nitrogen-rich heterocyclic anions and a preparation method thereof, belonging to the field of energy-containing materials.

Background

Cationic Metal Organic Frameworks (CMOFs) are of interest for their potential applications in anion exchange and separation, catalysis, drug delivery, magnetism, electrical conductivity, and energetic materials. Chemically, CMOFs can be divided into three parts: a coordinating metal cation, a neutral organic ligand and a backbone-balancing anion. Traditionally, the structure and properties of CMOFs have been mainly modulated by the choice of a large number of metal ions or organic ligands. Recently, some reports have shown that changing the counter anion in the framework can also tune its properties. However, the types of anions available as counter anions are limited, and most of these anions are inorganic anions, whose properties cannot be further adjusted by functionalization. Therefore, it is highly desirable to develop a new class of CMOFs with functionalized organic anions as counter anions.

Five-membered nitrogen-enriched azoles such as imidazole, pyrazole, triazole and tetrazole have acidic N-H bonds and are easily dehydrogenated to form corresponding nitrogen-enriched heterocyclic anions (salts) through simple replacement reaction. In addition, they contain a small number of potentially functionalized nitrogen and carbon atoms in the azole ring, and more functional group-modified nitrogen-rich heterocyclic anions can be generated by introducing different groups (such as amino, nitro, etc.). In particular, nitrogen-rich heterocyclic anions have a higher nitrogen content and a higher heat of positive formation (e.g., heat of formation Δ H) than inorganic anions_f°/kJ·mol^-1Triazolate is +109.0, tetrazolate is +237.2, nitrate is-307.9, perchlorate is-227.8), so their salts are often used in energetic materials. In this case, if the nitrogen-rich heterocyclic anion is to be usedOr functional group modified nitrogen-rich heterocyclic anions are introduced into the frames of the CMOFs as charge balancing anions, so that the energy-containing COMFs material with unique energy characteristics can be obtained. However, the inventors have tried to combine the ammonium salt solution of 5-nitrotetrazole with the solution of inorganic copper salt to form a copper precipitate of 5-nitrotetrazole immediately, since the nitrogen-rich heterocyclic anions contain many sp2 nitrogen donor atoms and have a strong coordinating ability to metal ions, making them difficult to store as counter anions in the framework. The design and fabrication of materials containing capable COMFs remains a significant challenge.

Disclosure of Invention

In view of the above, the present invention aims to provide a two-dimensional energy-containing CMOFs material containing nitro nitrogen-rich heterocyclic anions and a preparation method thereof.

In order to achieve the purpose, the technical scheme of the invention is as follows:

the two-dimensional energetic CMOFs material containing nitro nitrogen-rich heterocyclic anions comprises coordination metal cations, neutral organic ligands and skeleton balancing anions, wherein the coordination metal cations are transition metal copper ions, cobalt ions, zinc ions or iron ions, and the neutral organic ligands are energetic organic ligands with high nitrogen content, namely 4, 4' -azo-1, 2,4-triazole (ATRZ, molecule C)₄H₄N₈And the nitrogen content is 68.4%), and the skeleton balancing anion is a series of nitrogen-rich heterocyclic ring (pyrazole, triazole, tetrazole and the like) energetic anions containing 1-3 nitro groups.

Preferably, when the metal cation is copper, the backbone counter anion is 5-nitrotetrazole anion (NTT)^-)3, 5-dinitro-1,2, 4-triazole anion (DNT)^-)3,4, 5-trinitropyrazole anion (TNP)^-5-nitrotetrazole-2N-oxide anion (NTTO)^-3,5-dinitro-1,2, 4-triazole-1N-oxide anion (DNTO)^-) And 3,4, 5-trinitropyrazole-1N-oxide anion (TNPO)^-) One or more of (1); when the metal cation is cobalt ion, the backbone counter anion is NTT^-And/or DNT^-(ii) a When the metal cation is zinc ion, the skeletonThe counter anion is DNT^-(ii) a When the metal cation is iron, the backbone counter anion is DNT^-。

A preparation method of two-dimensional energetic CMOFs material containing nitro nitrogen-rich heterocyclic anions comprises the following steps:

adding a nitrogen-rich heterocyclic anionic salt solution containing 1-3 nitro groups and an inorganic metal salt solution into an ATRZ aqueous solution, uniformly mixing, and stirring at 25-30 ℃ for 0.5-2 h; after stirring, filtering, collecting filtrate, standing at room temperature until crystals are completely separated out, filtering out the crystals, washing with water, and drying in vacuum to obtain the two-dimensional energy-containing CMOFs material containing the nitro nitrogen-rich heterocyclic anions;

wherein the molar ratio of ATRZ, the nitrogen-rich heterocyclic anion salt and the inorganic metal salt is 3:0.2: 3-3: 4: 3;

the inorganic metal salt is copper salt, cobalt salt, zinc salt or ferrous salt.

Preferably, when the inorganic metal salt is a copper salt, the nitrogen-rich heterocyclic anion salt containing a nitro group is one or more of 5-nitrotetrazole ammonium salt (NTTA), 3,5-dinitro-1,2, 4-triazole ammonium salt (DNTA), 3,4,5-trinitropyrazole ammonium salt (TNPA), 5-nitrotetrazole-2N-ammonium oxide salt (NTTOA), 3,5-dinitro-1,2, 4-triazole-1N-ammonium oxide salt (DNTOA), and 3,4, 5-trinitropyrazole-1N-ammonium oxide salt (TNPOA);

when the inorganic metal salt is a cobalt salt, the nitrogen-rich heterocyclic anion salt containing the nitro is NTTA and/or DNTA;

when the inorganic metal salt is cobalt salt or ferrous salt, the nitrogen-rich heterocyclic anion salt containing the nitro is DNTA. .

Preferably, the addition sequence is ATRZ aqueous solution, nitrogen-rich heterocyclic anion salt solution and inorganic metal salt solution when mixing. It is desirable to avoid prior preferential mixing of the nitrogen-rich heterocyclic anion salt and the inorganic metal salt solution.

Preferably, the molar ratio of ATRZ, the nitrogen-rich heterocyclic anion salt and the inorganic metal salt is 3:1.5: 3-3: 3: 3.

Preferably, the solution molar concentration of the ATRZ, the nitrogen-rich heterocyclic anion salt and the inorganic metal salt is 0.1-0.4 mol/L.

Preferably, the standing time is 3-7 days. Usually, a small amount of blocky transparent crystals begin to precipitate after standing for 6-8 hours, and the crystals can completely precipitate after continuously standing for 3-7 days.

Preferably, the drying temperature is 50-80 ℃, and the drying time is 5-7 h.

Preferably, the copper salt is Cu (BF)₄)₂·6H₂O、Cu(NO₃)₂·3H₂O and CuSO₄·5H₂O or more; the cobalt salt is Co (NO)₃)₂·5H₂O and/or Co (BF)₄)₂·5H₂O; the zinc salt is Zn (ClO)₄)₂·6H₂O and/or Zn (NO)₃)₂·6H₂O; the ferrous salt is FeSO₄·7H₂O and/or Fe (NO)₃)₂。

Advantageous effects

According to the invention, a series of two-dimensional energy-containing CMOFs materials are obtained by specially selecting neutral energy-containing organic ligands, nitro-containing nitrogen-rich heterocyclic anion salts and inorganic metal salts; by mixing neutral energy-containing organic ligand ATRZ, nitrogen-rich heterocyclic anion salt containing nitro and inorganic metal salt and controlling reaction conditions, crystals with high crystallization degree and excellent quality are obtained, and the obtained product can be directly used for single crystal analysis.

The invention further adjusts the performance of the MOF material in terms of energy content by replacing the counter anions in the framework of the MOF material with nitrogen-rich heterocyclic anions containing nitro groups, wherein the energy-containing CMOFs material has higher density, higher nitrogen oxygen content and higher detonation heat.

According to the invention, the ATRZ and the transition metal cations (copper ions, cobalt ions, zinc ions or ferrous ions) have extremely strong coordination interaction (which is attributed to the fact that a plurality of nitrogen atoms capable of coordinating in the chemical structure of the ATRZ exist), and direct coordination or insoluble salt formation between the nitrogen-rich heterocyclic anions and the metal cations is avoided, so that the whole system can be kept clear and stable in a certain time, and the two-dimensional energy-containing CMOFs material containing the nitro nitrogen-rich heterocyclic anions is finally formed along with the increase of the time.

In the invention, ATRZ and transition metal ions are selected to form a two-dimensional energetic CMOFs cation framework. The greatest benefit of this framework is that the molecular length of ATRZ as a ligand is large enough, which makes the resulting MOFs material have large enough cavities to contain and fix the nitrogen-rich heterocyclic anions, and at the same time, makes the structure more stable through electrostatic interaction between the cation framework and the nitrogen-rich heterocyclic anions.

In the invention, a dual energy-containing system is formed between an energy-containing cation framework formed by the neutral energy-containing organic ligand and the transition metal ions and a nitrogen-rich heterocyclic anion containing nitryl, and the energy-containing performance of the prepared CMOFs is further regulated and controlled.

Drawings

FIG. 1 shows the stacking structure of MOF (Cu-NTT) prepared in example 1 of the present invention along the crystallographic direction.

FIG. 2 shows the stacking structure of MOF (Cu-DNT) prepared in example 2 of the present invention along the crystallographic direction.

FIG. 3 shows the stacking structure of MOF (Cu-TNP) prepared in example 3 of the present invention along the crystallographic direction.

FIG. 4 shows the stacking structure of MOF (Cu-NTTO) prepared in example 4 of the present invention along the crystallographic direction.

FIG. 5 shows the stacking structure of MOF (Cu-DNTO) prepared in example 5 of the present invention along the crystallographic direction.

FIG. 6 shows the stacking structure of MOF (Cu-TNPO) prepared in example 6 of the present invention along the crystallographic direction.

FIG. 7 shows the stacking structure of MOF (Co-NTT) prepared in example 7 of the present invention along the crystallographic direction.

FIG. 8 shows the stacking structure of MOF (Co-DNT) prepared in example 8 of the present invention along the crystallographic direction.

FIG. 9 shows the crystallographic orientation stacking structure of MOF (Zn-DNT) prepared in example 9 of the present invention.

FIG. 10 shows the stacking structure of MOF (Fe-DNT) prepared in example 10 of the present invention along the crystallographic direction.

FIG. 11 is a crystal coordination environment diagram of MOF (Cu-NTT) prepared in example 1 of the present invention.

FIG. 12 is a crystal coordination environment diagram of MOF (Cu-DNT) prepared in example 2 of the present invention.

FIG. 13 is a crystal coordination environment diagram of MOF (Cu-TNP) prepared in example 3 of the present invention.

FIG. 14 is a crystal coordination environment diagram of MOF (Cu-NTTO) prepared in example 4 of the present invention.

FIG. 15 is a crystal coordination environment diagram of MOF (Cu-DNTO) prepared in example 5 of the present invention.

FIG. 16 is a crystal coordination environment diagram of MOF (Cu-TNPO) prepared in example 6 of the present invention.

FIG. 17 is a crystal coordination environment diagram of MOF (Co-NTT) prepared in example 7 of the present invention.

FIG. 18 is a crystal coordination environment diagram of MOF (Co-DNT) prepared in example 8 of the present invention.

FIG. 19 is a diagram showing the crystal coordination environment of MOF (Zn-DNT) prepared in example 9 of the present invention.

FIG. 20 is a crystal coordination environment diagram of MOF (Fe-DNT) prepared in example 10 of the present invention.

FIG. 21 is a thermogravimetric-differential scanning calorimetry (TG-DSC) curve of MOF (Cu-DNT) crystals prepared in example 2 of the present invention.

FIG. 22 is a TG-DSC curve of MOF (Cu-TNP) crystals prepared in example 3 of the present invention.

FIG. 23 is a TG-DSC curve of MOF (Cu-DNTO) crystals prepared in example 5 of the present invention.

FIG. 24 is a TG-DSC curve of MOF (Cu-TNPO) crystals prepared in example 6 of the present invention.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

In the following examples:

(1) the synthesis of ATRZ was carried out according to the method described in "Li S H, Pang S P, Li X T, et al.Synthesis of new tetrazene (N-N ═ N-N) -linked bi (1,2, 4-triazine) [ J ]. Kunststoff-Kagaku (English edition), 2007, 18(10): 1176-.

(2) Synthesis of 5-nitrotetrazolium ammonium salt (NTTA) according to the literature "T M,Mayer P,MiróS C,et al.Simple,nitrogen-rich,energetic salts of 5-nitrotetrazole[J]Inorganic Chemistry,2008,47(13): 6014. 6027 ".

(3) Synthesis of3,5-dinitro-1,2, 4-triazolylammonium salts (DNTA) was prepared as described in the literature "Haiges R, Chabot G B, Kaplan S M, et al Synthesis and structural characterization of3,5-dinitro-1,2,4-triazolates [ J ]. Dalton trains, 2015,44(7): 2978-.

(4) Synthesis of3, 4,5-Trinitropyrazole ammonium salt (TNPA) was prepared as described in the literature "Zhang Y, Guo Y, Joo Y, et al.3,4,5-Trinitropyrazole-based energetic salts [ J ]. Chemistry: A European Journal,2010,16(35): 10778-.

(5) Synthesis of 5-nitrotetrazole-2N-ammonium oxide salts (NTTOA) was prepared as described in the literature "Michael G M, Klapotke D G, et al, Nitratroazolate-2N-oxides and the protocol of N-oxide interaction [ J ]. Journal of the American Chemical Society,2010,132(48): 17216-26".

(6) Synthesis of3, 4, 5-trinitropyrazole-1N-ammonium oxide salt (TNPOA) was prepared as described in the literature "Zhang Y, Parrish D A, Shreeve J M. Synthesis and Properties of3, 4,5-trinitropyrazole-1-ol and its energetic salts [ J ]. Journal of Materials Chemistry,2012,22(25): 12659-.

(7) Preparation of3,5-dinitro-1,2, 4-triazole-1N-ammonium oxide (DNTOA) referring to the preparation method of TNPOA, TNPA is replaced by DNTA, and the reaction temperature is increased to 50 ℃.

(8) The principle of the method of the invention is as follows:

example 1

(1) 1.5mmol of ATRZ ligand (0.246g) was added to 10mL of H₂Heating to 65 ℃ in O, and stirring until the ATRZ is completely dissolved to obtain an ATRZ solution;

(2) 1mmol of the salt NTTA (0.133g) of the nitrogen-rich heterocyclic anion with nitro groups was added to 5mL of H₂Heating to 65 ℃ in O, and stirring until the NTTA is completely dissolved to obtain an NTTA solution;

(3) 1.5mmol of the inorganic metal salt Cu (BF)₄)₂·6H₂O (0.517g) was added to 5mL of H₂Dissolving in O to obtain Cu (BF)₄)₂A solution;

(4) adding NTTA solution dropwise into ATRZ solution, and then adding Cu (BF) dropwise₄)₂Stirring the solution at 25 ℃ for 0.5h, filtering after stirring, collecting filtrate, standing at room temperature for 3 days until blue crystals are completely separated out, carrying out suction filtration, washing the crystals with water for 3 times, and carrying out vacuum drying at 65 ℃ for 6h to obtain a two-dimensional energetic CMOFs material (MOF (Cu-NTT)) containing nitro nitrogen-rich heterocyclic anions; the yield is 70.23%; the stacking structure of the material along the crystallographic direction is shown in FIG. 1, the crystal coordination environment of the material is shown in FIG. 11, and the single crystal performance parameters of the material are shown in Table 1.

Example 2

(1) 1.5mmol of ATRZ ligand (0.246g) was added to 10mL of H₂Heating to 65 ℃ in O, and stirring until the ATRZ is completely dissolved to obtain an ATRZ solution;

(2) 1mmol of the salt DNTA (0.176g) of the nitrogen-rich heterocyclic anion with nitro groups was added to 5mL of H₂Heating to 65 ℃ in O, and stirring until the DNTA is completely dissolved to obtain a DNTA solution;

(3) 1.5mmol of the inorganic metal salt Cu (NO)₃)₂·3H₂O (0.360g) was added to 5mL of H₂Dissolving in O to obtain Cu (NO)₃)₂A solution;

(4) firstly, dripping DNTA solution into ATRZ solution, and then dripping Cu (NO)₃)₂Stirring the solution at 25 deg.C for 0.5h, filtering, collecting filtrate, standing at room temperature for 3 days until blue crystals are completely separated out, vacuum filtering, washing the crystals with water for 3 times at 65 deg.CVacuum drying for 6h to obtain a two-dimensional energy-containing CMOFs material (MOF (Cu-DNT)) containing nitro nitrogen-rich heterocyclic anions; the yield was 69.73%; the stacking structure of the material along the crystallographic direction is shown in FIG. 2, the crystal coordination environment of the material is shown in FIG. 12, the single crystal performance parameters of the material are shown in Table 1, the TG-DSC curve of the material is shown in FIG. 21, and the analysis results are shown in Table 3.

Example 3

(1) 1.5mmol of ATRZ ligand (0.246g) was added to 10mL of H₂Heating to 65 ℃ in O, and stirring until the ATRZ is completely dissolved to obtain an ATRZ solution;

(2) 1mmol of nitrogen-rich heterocyclic anion salt TNPA with nitro group (0.220g) was added to 5mL of H₂Heating to 65 ℃ in O, and stirring until the TNPA is completely dissolved to obtain a TNPA solution;

(3) 1.5mmol of inorganic metal salt CuSO₄·5H₂O (0.375g) was added to 5mL of H₂Dissolving in O to obtain CuSO₄A solution;

(4) adding TNPA solution dropwise into ATRZ solution, and then adding CuSO dropwise₄Stirring the solution at 25 ℃ for 0.5h, filtering after stirring, collecting filtrate, standing at room temperature for 5 days until purple crystals are completely separated out, carrying out suction filtration, washing the crystals with water for 3 times, and carrying out vacuum drying at 60 ℃ for 8h to obtain a two-dimensional energy-containing CMOFs material (MOF (Cu-TNP)) containing nitro nitrogen-rich heterocyclic anions; the yield was 71.34%; the stacking structure of the material along the crystallographic direction is shown in FIG. 3, the crystal coordination environment of the material is shown in FIG. 13, the single crystal performance parameters of the material are shown in Table 1, the TG-DSC curve of the material is shown in FIG. 22, and the analysis results are shown in Table 3.

Example 4

In this example, the salt of the nitrogen-rich heterocyclic anion with nitro group is 1mmol NTTOA (0.149g), and the rest of the experimental operations are the same as those in example 1, so that a two-dimensional energy-containing CMOFs material (MOF (Cu-NTTO)) containing the nitrogen-rich heterocyclic anion with nitro group is prepared, and the yield is 71.55%; the stacking structure of the material along the crystallographic direction is shown in FIG. 4, the crystal coordination environment of the material is shown in FIG. 14, and the single crystal performance parameters of the material are shown in Table 1.

Example 5

In this example, the salt of the nitrogen-rich heterocyclic anion with nitro group is 1mmol of DNTOA (0.192g), and the rest of the experimental operations are the same as those in example 1, so that a two-dimensional energetic CMOFs material (MOF (Cu-DNTO)) containing the nitrogen-rich heterocyclic anion with nitro group is prepared, and the yield is 72.16%; the stacking structure of the material along the crystallographic direction is shown in FIG. 5, the crystal coordination environment of the material is shown in FIG. 15, the single crystal performance parameters of the material are shown in Table 1, the TG-DSC curve of the material is shown in FIG. 23, and the analysis results are shown in Table 3.

Example 6

In this example, the salt of the nitrogen-rich heterocyclic anion with nitro group is 1mmol of TNPOA (0.236g), and the rest of the experimental operations are the same as those in example 1, so that a two-dimensional energy-containing CMOFs material (MOF (Cu-TNPO)) containing the nitrogen-rich heterocyclic anion with nitro group is prepared, and the yield is 72.08%; the stacking structure of the material along the crystallographic direction is shown in FIG. 6, the single crystal performance parameters of the material are shown in Table 2, the crystal coordination environment of the material is shown in FIG. 16, the TG-DSC curve of the material is shown in FIG. 24, and the analysis results are shown in Table 3.

Example 7

The inorganic metal salt in this example was 1.5mmol Co (NO)₃)₂·6H₂O (0.436g), and the rest of the experimental procedures are the same as in example 1, to prepare a two-dimensional energetic CMOFs material (MOF (Co-NTT)) containing nitro nitrogen-rich heterocyclic anions with a yield of 70.72%; the stacking structure of the material along the crystallographic direction is shown in FIG. 7, the crystal coordination environment of the material is shown in FIG. 17, and the single crystal performance parameters of the material are shown in Table 2.

Example 8

In this example, the nitrogen-rich heterocyclic anion salt with a nitro group was 1mmol of DNTA (0.176g), and the inorganic metal salt was 1.5mmol of Co (BF)₄)₂·6H₂O (0.511g), otherwise the same as in example 7, gave a two-dimensional, energy-containing CMOFs material (MOF (Co-DNT)) containing nitro, nitrogen-rich heterocyclic anions in an yield of 73.56%; the stacking structure of the material along the crystallographic direction is shown in FIG. 8, the crystal coordination environment of the material is shown in FIG. 18, and the single crystal performance parameters of the material are shown in Table 2.

Example 9

In this example, the nitrogen-rich heterocyclic anion salt with a nitro group was 1mmol of DNTA (0.176g), and the inorganic metal salt was 1.5mmol of Zn (ClO)₄)₂·6H₂O (0.558g) or Zn (NO)₃)₂·6H₂O (0.446g), otherwise as in example 1, a two-dimensional energetic CMOFs material containing nitro nitrogen-rich heterocyclic anions (MOF (Zn-DNT)) was prepared in 74.78% and 74.55% yields, respectively; the stacking structure of the material along the crystallographic direction is shown in FIG. 9, the crystal coordination environment of the material is shown in FIG. 19, and the single crystal performance parameters of the material are shown in Table 2.

Example 10

In this example, the nitrogen-rich heterocyclic anion salt with nitro group was 1mmol of DNTA (0.176g) and the inorganic metal salt was 1.5mmol of FeSO₄·7H₂O (0.417g) or Fe (NO)₃)₂(0.270g) A two-dimensional energetic CMOFs material (MOF (Fe-DNT)) containing nitro nitrogen-rich heterocyclic anions was prepared in the same manner as in example 1, with yields of 72.66% and 70.37%, respectively. The stacking structure of the material along the crystallographic direction is shown in FIG. 10, the crystal coordination environment of the material is shown in FIG. 20, and the single crystal performance parameters of the material are shown in Table 2.

The 10 kinds of energy-containing CMOFs crystals prepared in the examples are subjected to corresponding single crystal X-ray diffraction analysis test, thermal stability DSC-TG test and energy-containing performance characterization. The single crystal X-ray diffraction analysis test results show that the CMOFs crystals prepared in examples 1-10 are two-dimensional energetic CMOFs, and the performance parameter results are shown in tables 1-2.

TABLE 1

TABLE 2

The materials described in example 2, example 4, example 5 and example 6 were mixed with a common inorganic anionic energetic MOF (Cu-NO)₃) The results of comparative analyses of the properties of the conventional explosives TNT, RDX and CL-20 are shown in Table 3.

TABLE 3

In the table, the number of the first and second,^ainitial decomposition temperature (DSC, ° c);^bdensity (g cm) measured by gas gravimeter^-3)；^cDensity of X-ray diffraction analysis (g cm)^-3)；^dThe oxygen content;^etotal oxygen and nitrogen content;^fimpact sensitivity (J);^ga friction sensitivity (N);^helectrostatic sensitivity (J);ⁱexperimental determination (oxygen bomb calorimetry) of the constant volume energy (kJ mol) of combustion^-1)；^jExperimental determination (according to-. DELTA._cU is repeatedly calculated) enthalpy of formation (kJ mol)^-1)；^kDetonation pressure (GPa);^ldetonation velocity (m s)^-1)；^mExplosion temperature (K);ⁿgas production volume after explosion (L kg)^-1)；^pDetonation Heat (kJ kg)^-1)；^qCalculating the detonation velocity and detonation pressure according to the single crystal density;^rthe various performance parameters of TNT and RDX are derived from published reports; all detonation parameters, including detonation pressure, detonation velocity, detonation temperature, detonation heat and gas production, were calculated from EXPLO5 v 6.01.

The results of table 1 were analyzed, specifically:

(1) density: the density of the two-dimensional energy-containing CMOFs is measured and is 1.75-1.84 g/cm³In the range of higher than the energy-containing MOF (Cu-NO) taking inorganic nitrate anions as balance anions₃) Density of (1.64 g/cm)³). Wherein the density of MOF (Cu-TNP) is up to 1.84g/cm³. The relatively high density may be due to extensive intermolecular hydrogen bonding in these crystals of CMOFs.

(2) Nitrogen and oxygen content: these CMOF have a significantly high nitrogen and oxygen content. The nitrogen and oxygen content is 70.26-72.97%, which is higher than MOF (Cu-NO)₃) 67.7% of.

(3) Explosion heating: the patent is based on experimental determination of (. DELTA. -)_cU) enthalpy of formation and density measured by experiments, EXPLO5 v6.01 software is adopted to calculate the detonation heat of the high-energy CMOFs, and the obtained detonation heat is between 4923 and 7375kJ/kg and is superior to MOF (Cu-NO)₃) (4562 kJ/kg). Especially the detonation heat of MOF (CuTNPO) is 7375kJ/kg, even higher than the strongest organic explosive CL-20(6168 kJ/kg). This is attributable to the fact that the anions in the CMOFs contain nitro groups rich in oxygen, as well as nitrogen-rich ATRZ ligands, and thus have a higher density, a higher nitrogen content and a better oxygen balance, which contribute to the release of more energy during the detonation process.

(4) Thermal stability: thermogravimetric-differential scanning calorimetry (TG-DSC) analysis is carried out on the newly prepared two-dimensional energetic CMOFs crystal, and TG analysis of a powder sample shows that gradual weight loss between 50 and 150 ℃ is attributed to solvation and release of coordinated water molecules. At the temperature range of 180-280 ℃, the main weight loss is caused by the decomposition of nitrogen-rich heterocyclic anions containing nitryl and ATRZ ligand and the collapse of a framework. TG-DSC analysis clearly shows that the initial decomposition temperature of these CMOFs materials is between 186 ℃ and 223 ℃.

(5) Sensitivity: for safety testing, the sensitivity of each two-dimensional high-energy CMOFs to impact and friction was also measured using a standard BAM drop hammer and BAM friction tester. Compared with RDX (7.5J), the impact sensitivity (8-23J) of the high-energy CMOFs material is smaller, and the friction sensitivity is larger than 48N.

The method successfully realizes the introduction of nitrogen-rich heterocyclic anions (with functional group modification) as additional balance anions in the CMOFs, and successfully prepares 10 two-dimensional energy-containing CMOFs crystals of 6 MOFs (Cu-Ar), 2 MOFs (Co-Ar), 1 MOF (Zn-Ar) and 1 MOF (Fe-Ar). By such simple operationThe preparation of various nitrogen-rich heterocyclic anion energy-containing CMOFs materials with nitryl is realized under mild reaction conditions, which belongs to the field of energy-containing MOFs materials for the first time. Moreover, the method shows a wide range of substrates, and can also be applied to various nitroheterocyclic anion salts, nitrogen oxides thereof and various transition metal salts. In addition, compared with inorganic anionic energetic CMOFs, the energetic CMOFs material obtained by the invention has higher density, higher nitrogen oxygen content and higher detonation heat. In particular, the MOF (TNPO) has a high density (1.84 g/cm)³) Acceptable sensitivity (IS:13J, FS:72N), relatively good oxygen balance (-9.16%), and good detonation heat (7636 kJ/kg). These results indicate that these new CMOFs are potential high energy density materials. The invention opens up a new way for the application of the nitrogen-rich heterocyclic anion modified by the functional group in the MOF material, considers the wide diversity of the nitro nitrogen-rich heterocyclic anion, and simultaneously provides a simple, convenient and effective method for developing novel high-energy CMOFs materials, thereby having wide application prospect.

In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.