A copper-containing hydrogen bond organic framework material and its preparation method and application

Abstract

The present invention discloses a copper-containing hydrogen-bond organic framework material, a preparation method, and an application thereof. The method comprises the following steps: mixing trimesic acid, melamine, and a copper salt and dispersing them in a solvent to obtain a mixed suspension; transferring the mixed suspension to a reactor for reaction to obtain a copper-containing hydrogen-bond organic framework material solution; cooling the copper-containing hydrogen-bond organic framework material solution, centrifuging it, and then post-treating the copper-containing hydrogen-bond organic framework material solid obtained by centrifugation to obtain a copper-containing hydrogen-bond organic framework material with a one-dimensional rod-shaped structure. When used in the thermal decomposition catalysis of ammonium perchlorate, the copper-containing hydrogen-bond organic framework material prepared by the present invention can exhibit high catalytic activity and stability, thereby concentrating the exothermic temperature range and heat release of ammonium perchlorate.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and in particular relates to a copper-containing hydrogen bond organic framework material and a preparation method and application thereof. Background Art

[0002] Ammonium perchlorate (AP) is the most widely used oxidizer in composite solid propellants, typically comprising 60% to 90% of the total propellant mass. Therefore, the reaction rate, activation energy, and thermal decomposition temperature of AP directly influence the propellant's combustion stability, combustion velocity, and energy output. A common approach to regulating AP thermal decomposition properties is to add a catalytically active catalyst, known as a combustion catalyst. Combustion catalysts have become a core functional component of solid propellants. The search for catalysts with enhanced catalytic activity for AP thermal decomposition has attracted increasing attention in the field of AP-based composite solid rocket propellants. With the rise of nanotechnology, numerous studies have reported on the use of nanoscale transition metals and their oxides to lower the thermal decomposition temperature of AP. However, nanocatalysts tend to aggregate, resulting in a reduction in available active sites and catalytic efficiency. Therefore, recent research has often used two- or three-dimensional porous materials to support nanocatalysts to address the agglomeration issue. While these approaches have achieved some success, they still suffer from limitations such as limited large-scale preparation, uneven loading, and low active component utilization. Therefore, new catalysts with uniform and completely monodispersed active component loading are needed to improve catalytic activity.

[0003] Hydrogen-bonded organic frameworks (HOFs) are a new type of crystalline material composed of organic units assembled through hydrogen bonding. These frameworks can be further stabilized by other weak interactions, such as π-π and van der Waals interactions. HOFs possess an inherent hydrogen-bonding network and hold great potential as proton-conducting materials. However, research on the catalytic activity of HOFs in solid rocket propellants remains limited, based on currently reported literature. Summary of the Invention

[0004] The present invention aims to overcome the deficiencies in the prior art and provide a copper-hydrogen-bonded organic framework material, a preparation method thereof, and applications thereof. The prepared copper-hydrogen-bonded organic framework material, when used in the thermal decomposition catalysis of ammonium perchlorate, can exhibit high catalytic activity and stability, thereby concentrating the exothermic temperature range and heat release of ammonium perchlorate.

[0005] The present invention provides the following technical solutions:

[0006] In a first aspect, a method for preparing a copper-containing hydrogen bond organic framework material is provided, comprising the following steps:

[0007] Mixing trimesic acid, melamine and copper salt and dispersing them in a solvent to obtain a mixed suspension;

[0008] Transferring the mixed suspension to a reactor for reaction to obtain a copper-containing hydrogen bond organic framework material solution;

[0009] The copper-hydrogen-bond organic framework material solution is cooled and centrifuged, and then the copper-hydrogen-bond organic framework material solid obtained by centrifugation is post-treated to obtain a copper-hydrogen-bond organic framework material with a one-dimensional rod-like structure.

[0010] Furthermore, the molar ratio of trimesic acid, melamine and copper salt is 1:1:(0.1~0.5).

[0011] Furthermore, the copper salt is a divalent salt, including any one of nitrate, perchlorate, hydrochloride, sulfate, and acetate.

[0012] Furthermore, the solvent includes any one of methanol, ethanol, and isopropanol.

[0013] Furthermore, the mixed suspension is reacted in the reactor at a temperature of 50-150° C. and a reaction time of 2-12 h.

[0014] Furthermore, the centrifugal speed is 5000-12000 rpm, and the centrifugal time is 5-30 min.

[0015] Furthermore, the post-treatment includes washing and freeze-drying the copper-containing hydrogen bond organic framework material solid; the solvent used for the washing includes any one of methanol, ethanol, and isopropanol, preferably a dispersion solvent of benzenetricarboxylic acid, melamine and copper salt.

[0016] In a second aspect, a copper-containing hydrogen bond organic framework material is provided, which is prepared using the method described in the first aspect.

[0017] In a third aspect, a method is provided for using the copper-containing hydrogen bond organic framework material described in the second aspect in the catalysis of thermal decomposition of ammonium perchlorate.

[0018] Furthermore, the amount of the copper-containing hydrogen bond organic framework material is 1% to 5% of the total mass of the mixture of ammonium perchlorate and the copper-containing hydrogen bond organic framework material.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) The copper-containing hydrogen bond organic framework material prepared by the present invention has metal ions uniformly embedded in the HOF framework in the form of ligands, which can better protect the high dispersion of the catalytic active centers and avoid their migration and aggregation during the catalytic process, so that the catalyst exhibits higher catalytic activity and stability. The preparation process is simple, mild, low-cost, and easy to achieve large-scale production.

[0021] (2) The one-dimensional rod-shaped copper-containing hydrogen bond organic framework material provided by the present invention contains a large number of carboxyl groups and amino groups. The lone pair electrons on the amino N and carbonyl O groups can make the copper-containing hydrogen bond organic framework material better distributed on the surface of AP particles, thereby improving the catalytic activity;

[0022] (3) When the copper-hydrogen bond organic framework material provided by the present invention is used in the catalysis of the thermal decomposition of ammonium perchlorate, Cu first catalyzes the decomposition of the HOF framework structure and releases heat locally quickly and in large quantities, promoting the decomposition and heat release of AP near the exothermic point; after the HOF framework structure decomposes, the active Cu sites are exposed and directly contact AP, further catalyzing the decomposition of AP, thereby making the exothermic temperature range and heat release of AP more concentrated. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 XRD comparison diagram of Cu-HOF and HOF prepared in Example 1 of the present invention;

[0024] Figure 2 This is a SEM test image of the Cu-HOF prepared in Example 1 of the present invention;

[0025] Figure 3 TEM test image of Cu-HOF prepared in Example 1 of the present invention;

[0026] Figure 4 This is a test diagram of the apparent activation energy of the thermal decomposition of AP catalyzed by Cu-HOF prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0027] The present invention will be further described below in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention.

[0028] Example 1

[0029] S1. Trimesic acid, melamine, and copper nitrate were mixed in a molar ratio of 1:1:0.5 and dispersed in methanol to form a blue suspension.

[0030] S2. Transfer the suspension in S1 to a reactor and react at 80° C. for 12 hours to obtain a copper-hydrogen bond organic framework material solution.

[0031] S3. Cool the copper-hydrogen bond organic framework material solution in S2 to room temperature and then centrifuge it at a speed of 5000 rpm for 30 minutes to obtain a copper-hydrogen bond organic framework material solid.

[0032] S4. The copper-containing hydrogen bond organic framework material solid obtained in S3 is washed with methanol and freeze-dried to obtain a copper-containing hydrogen bond organic framework material (Cu-HOF) having a one-dimensional rod-like structure.

[0033] S5. Using the copper-hydrogen bond organic framework material obtained in S4 as an AP thermal decomposition catalyst, the added amount is 5% of the total mass of the mixture of ammonium perchlorate and the copper-hydrogen bond organic framework material.

[0034] Example 2

[0035] S1. Disperse trimesic acid, melamine, and copper chloride in isopropyl alcohol at a molar ratio of 1:1:0.1 to form a blue suspension.

[0036] S2. Transfer the suspension in S1 to a reactor and react at 150° C. for 2 h to obtain a copper-hydrogen bond organic framework material solution.

[0037] S3. Cool the copper-hydrogen bond organic framework material solution in S2 to room temperature and then centrifuge it at a speed of 12000 rpm for 30 minutes to obtain a copper-hydrogen bond organic framework material solid.

[0038] S4. Washing the obtained copper-containing hydrogen bond organic framework material solid with isopropanol and freeze-drying it to obtain a copper-containing hydrogen bond organic framework material with a one-dimensional rod-like structure.

[0039] S5. Using the obtained copper-containing hydrogen bond organic framework material as an AP thermal decomposition catalyst, the addition amount is 5% of the total mass of the mixture of ammonium perchlorate and the copper-containing hydrogen bond organic framework material.

[0040] Example 3

[0041] S1. Disperse trimesic acid, melamine, and copper acetate in isopropyl alcohol at a molar ratio of 1:1:0.3 to form a blue suspension.

[0042] S2. Transfer the suspension in S1 to a reactor and react at 50° C. for 12 hours to obtain a copper-hydrogen bond organic framework material solution.

[0043] S3. Cool the copper-hydrogen bond organic framework material solution in S2 to room temperature and then centrifuge it at a speed of 12000 rpm for 5 minutes to obtain a copper-hydrogen bond organic framework material solid.

[0044] S4. Washing the obtained copper-containing hydrogen bond organic framework material solid with isopropanol and freeze-drying it to obtain a copper-containing hydrogen bond organic framework material with a one-dimensional rod-like structure.

[0045] S5. Using the obtained copper-containing hydrogen bond organic framework material as an AP thermal decomposition catalyst, the addition amount is 3% of the total mass of the mixture of ammonium perchlorate and the copper-containing hydrogen bond organic framework material.

[0046] Example 4

[0047] S1. Disperse trimesic acid, melamine, and copper sulfate in ethanol at a molar ratio of 1:1:0.4 to form a blue suspension.

[0048] S2. Transfer the suspension in S1 to a reactor and react at 120° C. for 6 hours to obtain a copper-hydrogen bond organic framework material solution.

[0049] S3. Cool the copper-hydrogen bond organic framework material solution in S2 to room temperature and then centrifuge it at a speed of 8000 rpm for 30 minutes to obtain a copper-hydrogen bond organic framework material solid.

[0050] S4. Washing the obtained copper-containing hydrogen bond organic framework material solid with ethanol and freeze-drying it to obtain a copper-containing hydrogen bond organic framework material with a one-dimensional rod-like structure.

[0051] S5. Using the obtained copper-containing hydrogen bond organic framework material as an AP thermal decomposition catalyst, the addition amount is 2% of the total mass of the mixture of ammonium perchlorate and the copper-containing hydrogen bond organic framework material.

[0052] Example 5

[0053] S1. Disperse trimesic acid, melamine, and copper perchlorate in methanol at a molar ratio of 1:1:0.5 to form a blue suspension.

[0054] S2. Transfer the suspension in S1 to a reactor and react at 150° C. for 2 h to obtain a copper-hydrogen bond organic framework material solution.

[0055] S3. Cool the copper-hydrogen bond organic framework material solution in S2 to room temperature and then centrifuge it at a speed of 10,000 rpm for 20 minutes to obtain a copper-hydrogen bond organic framework material solid.

[0056] S4. Washing the obtained copper-containing hydrogen bond organic framework material solid with methanol and freeze-drying it to obtain a copper-containing hydrogen bond organic framework material with a one-dimensional rod-like structure.

[0057] S5. Using the obtained copper-hydrogen bond organic framework material as an AP thermal decomposition catalyst, the addition amount is 1% of the total mass of the mixture of ammonium perchlorate and the copper-hydrogen bond organic framework material.

[0058] Example 6

[0059] S1. Disperse trimesic acid, melamine, and copper nitrate in methanol at a molar ratio of 1:1:0.1 to form a blue suspension.

[0060] S2. Transfer the suspension in S1 to a reactor and react at 80° C. for 12 hours to obtain a copper-hydrogen bond organic framework material solution.

[0061] S3. Cool the copper-hydrogen bond organic framework material solution in S2 to room temperature and then centrifuge it at a speed of 5000 rpm for 30 minutes to obtain a copper-hydrogen bond organic framework material solid.

[0062] S4. Washing the obtained copper-containing hydrogen bond organic framework material solid with methanol and freeze-drying it to obtain a copper-containing hydrogen bond organic framework material with a one-dimensional rod-like structure.

[0063] S5. Using the obtained copper-containing hydrogen bond organic framework material as an AP thermal decomposition catalyst, the addition amount is 5% of the total mass of the mixture of ammonium perchlorate and the copper-containing hydrogen bond organic framework material.

[0064] Example 7

[0065] S1. Disperse trimesic acid, melamine, and copper nitrate in methanol at a molar ratio of 1:1:0.5 to form a blue suspension.

[0066] S2. Transfer the suspension in S1 to a reactor and react at 80° C. for 12 hours to obtain a copper-hydrogen bond organic framework material solution.

[0067] S3. Cool the copper-hydrogen bond organic framework material solution in S2 to room temperature and then centrifuge it at a speed of 5000 rpm for 30 minutes to obtain a copper-hydrogen bond organic framework material solid.

[0068] S4. Washing the obtained copper-containing hydrogen bond organic framework material solid with methanol and freeze-drying it to obtain a copper-containing hydrogen bond organic framework material with a one-dimensional rod-like structure.

[0069] S5. Using the obtained copper-hydrogen bond organic framework material as an AP thermal decomposition catalyst, the addition amount is 1% of the total mass of the mixture of ammonium perchlorate and the copper-hydrogen bond organic framework material.

[0070] Comparative Example 1

[0071] S1. Disperse trimesic acid and melamine in methanol at a molar ratio of 1:1 to form a white suspension.

[0072] S2. Transfer the suspension in S1 to a reactor and react at 80° C. for 12 hours to obtain a hydrogen bond organic framework material solution.

[0073] S3. Cool the hydrogen-bonded organic framework material solution in S2 to room temperature and then centrifuge it at a speed of 5000 rpm for 30 minutes to obtain a hydrogen-bonded organic framework material solid.

[0074] S4. Washing the obtained hydrogen-bonded organic framework material solid with ethanol and freeze-drying it to obtain a hydrogen-bonded organic framework material with a one-dimensional rod-like structure.

[0075] S5. Using the obtained hydrogen-bonded organic framework material as an AP thermal decomposition catalyst, the added amount is 5% of the total mass of the mixture of ammonium perchlorate and the hydrogen-bonded organic framework material.

[0076] Comparative Example 2

[0077] Copper oxide was used as a catalyst for the thermal decomposition of AP, with the addition amount being 2% of the total mass of the mixture of ammonium perchlorate and copper oxide. The copper oxide was prepared using the method described in the following literature: Luo Yuanxiang, Lu Lude, Liu Xiaoheng, Yang Xujie, Wang Xin. Preparation of Nano-CuO and Its Catalytic Performance for the Thermal Decomposition of NH4ClO4, Chinese Journal of Inorganic Chemistry, 2002, 18(12): 1211-1214.

[0078] Performance Characterization Example

[0079] (1) XRD tests were performed on the copper-containing hydrogen bond organic framework material (Cu-HOF) and hydrogen bond organic framework material (HOF) prepared in Example 1. The results are as follows: Figure 1 As shown. Figure 1 It can be seen that when 2θ is between 10° and 15°, the peak shapes of HOF and Cu-HOF change slightly, indicating that the addition of copper does affect the crystal structure of HOF; however, when 2θ is between 15° and 45°, the peak shapes of HOF and Cu-HOF are consistent, indicating that the addition of copper has no effect on the main structure of HOF.

[0080] (2) The Cu-HOF prepared in Example 1 was characterized by SEM and TEM. Figure 2 As shown, before SEM testing, the sample was platinum-plated to enhance the conductivity of the sample. The acceleration voltage was 5 kV and the magnification was 50,000. The results showed that the Cu-HOF prepared in Example 1 was a one-dimensional rod-like structure. Figure 3 As shown, the acceleration voltage of TEM characterization is 200 kV, and the results also show that the Cu-HOF prepared in Example 1 is a one-dimensional rod-like structure.

[0081] (3) If Figure 4 The figure shows the apparent activation energy test diagram of the thermal decomposition of AP catalyzed by Cu-HOF prepared in Example 1. Figure 4 It can be seen that compared with pure AP, the activation energy of material decomposition is significantly reduced after adding the catalyst, which is consistent with its catalytic effect.

[0082] (4) The samples (ammonium perchlorate and copper-containing hydrogen bond organic framework material mixture) were subjected to TG and DSC tests using the methods described in Examples 1 to 7 and Comparative Examples 1 to 2. The sample test amount was 5 to 10 mg. The high-temperature decomposition peak and heat release were measured. The results are shown in Table 1 below:

[0083] Table 1 Comparison of high temperature decomposition peaks and heat release of examples and comparative examples

[0084]

[0085] As can be seen from Table 1, by comparing Example 1 and Comparative Example 1, it is found that the hydrogen bond framework material itself has a certain catalytic activity. Moreover, after the addition of copper salt, the catalytic effect is more obvious, the peak decomposition temperature is significantly reduced, and the heat release is also greatly increased, indicating that the hydrogen bond framework material and copper salt have a certain synergistic catalytic effect.

[0086] By comparing Example 4 and Comparative Example 2, it was found that under the same catalyst addition amount, the catalytic performance of the copper-containing hydrogen-bonded organic framework material of Example 4 was significantly better than the catalytic performance of the nano-copper oxide in the comparative example, which fully demonstrated the key role of the unique structure of the hydrogen-bonded organic framework material in catalysis.

[0087] The raw materials used in Examples 1, 6, and 7 are all trimesic acid, melamine, and copper nitrate, and the reaction solvent, reaction conditions, centrifugation conditions, washing, and drying are all the same. In Examples 1 and 7, except for the different addition amounts, all other conditions are the same. It can be seen that with a larger addition amount, the pyrolysis temperature decreases accordingly, and the heat release also increases. In Examples 1 and 6, except for the different molar ratios of trimesic acid, melamine, and copper nitrate, all other conditions are the same. It can be seen that with a higher molar ratio of copper nitrate, the pyrolysis temperature decreases accordingly, and the heat release also increases. This is because the number of metal active sites increases, significantly enhancing the catalytic effect during the AP decomposition process. In Examples 6 and 7, the molar ratios and addition amounts of trimesic acid, melamine, and copper nitrate are different, but by increasing the addition amount, the copper nitrate content can be increased to a consistent level, achieving the same catalytic effect. This indicates that the key lies in the number of metal active sites, and both methods are beneficial for increasing the number of metal active sites.

[0088] Examples 2, 3, 4, and 5 are the results of the decomposition of ammonium perchlorate catalyzed by hydrogen-bonding framework materials containing different copper salts, demonstrating that the anion of the copper salt has little effect on the catalytic process.

[0089] In summary, the catalytic effect of Cu-HOF is significantly improved compared with HOF and single nano-copper oxide, proving that the manifestation of this catalytic effect mainly depends on the unique material structure of Cu-HOF; it can also be seen from the examples that the catalytic effect has a significant correlation with the number of metal active sites and is less affected by copper salt anions.

[0090] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a copper-containing hydrogen bond organic framework material, characterized in that: The following steps are involved: Mixing trimesic acid, melamine and copper salt and dispersing them in a solvent to obtain a mixed suspension; Transferring the mixed suspension to a reactor for reaction to obtain a copper-containing hydrogen bond organic framework material solution; The copper-hydrogen-bond organic framework material solution is cooled and centrifuged, and then the copper-hydrogen-bond organic framework material solid obtained by centrifugation is post-treated to obtain a copper-hydrogen-bond organic framework material with a one-dimensional rod-like structure.

2. The method for preparing a copper-containing hydrogen bond organic framework material according to claim 1, wherein: The molar ratio of trimesic acid, melamine and copper salt is 1:1:(0.1-0.5).

3. The method for preparing a copper-containing hydrogen bond organic framework material according to claim 1, wherein: The copper salt includes any one of nitrate, perchlorate, hydrochloride, sulfate and acetate.

4. The method for preparing a copper-containing hydrogen bond organic framework material according to claim 1, wherein: The solvent includes any one of methanol, ethanol and isopropanol.

5. The method for preparing a copper-containing hydrogen bond organic framework material according to claim 1, wherein: The mixed suspension is reacted in a reactor at a temperature of 50-150° C. for a reaction time of 2-12 hours.

6. The method for preparing a copper-containing hydrogen bond organic framework material according to claim 1, wherein: The centrifugal speed is 5000-12000 rpm, and the centrifugal time is 5-30 min.

7. The method for preparing a copper-containing hydrogen bond organic framework material according to claim 1, wherein: The post-treatment includes washing and freeze-drying the copper-containing hydrogen bond organic framework material solid; the solvent used in the washing includes any one of methanol, ethanol, and isopropanol.

8. A copper-containing hydrogen bond organic framework material, characterized in that The method according to any one of claims 1 to 7 is used to prepare the product.

9. Use of the copper-containing hydrogen bond organic framework material according to claim 8 in catalysis of thermal decomposition of ammonium perchlorate.

10. Use of the copper-containing hydrogen bond organic framework material according to claim 9 in catalysis of thermal decomposition of ammonium perchlorate, characterized in that: The amount of the copper-containing hydrogen bond organic framework material is 1% to 5% of the total mass of the mixture of ammonium perchlorate and the copper-containing hydrogen bond organic framework material.

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