A graphene oxide-ferrocene composite and its preparation method

Abstract

The present invention discloses a graphene oxide-ferrocene composite and a preparation method thereof. The preparation process includes the following steps: 3-nitro-1,2,4-triazole-5-one reacts with N,N-dimethylaminomethyl ferrocene to synthesize an N,N-dimethylaminomethyl ferrocene 3-nitro-1,2,4-triazole-5-one compound; the N,N-dimethylaminomethyl ferrocene 3-nitro-1,2,4-triazole-5-one and graphene oxide are compounded to generate a graphene oxide-ferrocene composite. The graphene oxide-ferrocene composite synthesized by this method has a significant catalytic effect on the thermal decomposition of ammonium perchlorate (AP) and can be used as a combustion performance regulator in AP-based composite solid propellants.

Description

Technical Field

[0001] The present invention relates to a graphene oxide-ferrocene composite and a preparation method thereof, and the composite can be used as a combustion performance regulator in an AP-based composite solid propellant. Background Art

[0002] Missile rockets are important weapons in modern warfare and occupy an important position in the national defense layout of various countries. As the main power source of missile weapons, solid propellants convert chemical energy into heat energy through combustion in the combustion chamber, and then convert heat energy into the kinetic energy of rocket missiles through the nozzle. Therefore, the combustion performance of the propellant has a crucial impact on the performance of the weapon. At present, the relatively mature and efficient method is to add combustion catalysts to the propellant to improve its combustion performance.

[0003] At present, composite solid propellants with AP as the oxidizer have become the mainstream products due to their excellent comprehensive performance. Commonly used combustion catalysts include metals and their oxides, organometallic compounds, inorganic metal salts, etc. Among them, iron-based combustion catalysts are the most widely used. Common iron-based combustion catalysts include nano-ferric oxide and catocene.

[0004] Although the above two catalysts can effectively improve the thermal decomposition of AP, nano-ferric oxide is prone to agglomeration due to its large specific surface area, greatly reducing the catalytic efficiency of the catalyst, and the introduction of catocene will increase the sensitivity of the propellant to a certain extent, making it prone to accidental ignition during the preparation and storage of the propellant.

[0005] Therefore, there is an urgent need for a new type of combustion catalyst that can ensure its high catalytic efficiency while ensuring the safety of the propellant. Graphene oxide-based materials have a high specific surface area and excellent thermal and electrical conductivity, which can significantly affect the safety performance and combustion performance of energetic materials and show great application potential in the field of energetic materials. Summary of the Invention

[0006] The purpose of the present invention is to solve the deficiencies and defects of existing combustion catalysts for AP composite solid propellants, and provide a graphene oxide-ferrocene composite and a preparation method thereof. Without affecting the overall performance of the propellant itself, the combustion performance of the propellant is greatly improved.

[0007] The present invention is a graphene oxide-ferrocene composite, and the graphene oxide-ferrocene composite is a graphene oxide-N,N-dimethylaminomethyl ferrocene 3-nitro-1,2,4-triazole-5-one composite.

[0008] A synthesis method of a graphene oxide-ferrocene composite provided by the present invention includes the following steps:

[0009] (1) Preparation of N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one:

[0010] Dissolve 3-nitro-1,2,4-triazol-5-one completely in acetone, and at the same time dissolve N,N-dimethylaminomethylferrocene completely in acetone. Then slowly pour the N,N-dimethylaminomethylferrocene acetone solution into the 3-nitro-1,2,4-triazol-5-one acetone solution, stirring and mixing while pouring. Immediately, a yellow precipitate will form. After the precipitation is complete, filter and collect the yellow precipitate, and rinse it three times with ether. Then place it in a vacuum oven at 50 °C to dry to obtain the N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one compound powder; among them, the molar ratio of N,N-dimethylaminomethylferrocene to 3-nitro-1,2,4-triazol-5-one is 1.1 - 1.2;

[0011] (2) Preparation of graphene oxide suspension:

[0012] Disperse graphene oxide into ultrapure water and exfoliate it under ultrasound at 200 W until it is completely and evenly dispersed to obtain a graphene oxide suspension;

[0013] (3) Preparation of graphene oxide-ferrocene suspension:

[0014] Place the N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one prepared in step (1) into the graphene oxide suspension dispersed in step (2); place the mixture under ultrasound at 200 W and disperse it for 20 min, and then place the above mixture in a magnetic stirrer and stir magnetically for 20 min. After completion, obtain a graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one suspension;

[0015] (4) Preparation of graphene oxide-ferrocene composite:

[0016] Place the graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one suspension in step (3) under ultrasound at 200 W and disperse it for 20 min to obtain a homogeneous mixture of graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one. Place the above mixture in a petri dish and quickly freeze it into a block in an environment of -120 °C. Then place the above block in a freeze dryer. After complete drying, obtain a graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one composite, where the specific drying time depends on the water content in the graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one mixture.

[0017] The advantages of the present invention over the prior art are as follows:

[0018] The graphene oxide-ferrocene composite of the present invention is different from traditional catalysts. By adding 3-nitro-1,2,4-triazol-5-one, the catalyst is enriched with energetic components, preventing the reduction of the energy of the entire system due to the addition of the catalyst. Meanwhile, it ensures that the synthesized graphene oxide-ferrocene composite combines the planar structure of two-dimensional graphene oxide. Its numerous active sites and large specific surface area ensure the uniform dispersion of N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one. When the graphene oxide-ferrocene composite is used as a combustion catalyst, it can uniformly decompose to produce nano-iron oxide during the entire combustion process of the propellant, effectively avoiding the aggregation of nano-scale iron oxide. The synergistic effect of graphene oxide and ferrocene endows it with excellent catalytic performance. The graphene oxide-ferrocene composite of the present invention is synthesized by the method of vacuum freeze-drying, ensuring the uniformity of the composite while maintaining the integrity of the raw material structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 SEM pattern of the graphene oxide-ferrocene composite prepared in Example 1.

[0020] Figure 2 FTIR pattern of the graphene oxide-ferrocene composite prepared in Example 1.

[0021] Figure 3 DSC curves of AP before and after mixing with graphene oxide, ferrocene composite and the graphene oxide-ferrocene composite prepared in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0022] The morphology was characterized by a German ZEISS Sigma HD type scanning electron microscope, the infrared characterization was performed using a Japanese Shimadzu IRTracer-100 type Fourier transform infrared spectrometer, and the thermal decomposition of AP was characterized by a German NETZSCH DSC214 type differential scanning calorimeter.

[0023] The present invention will be further explained and illustrated below through specific examples.

[0024] Example 1

[0025] Synthesis of graphene oxide-ferrocene composite

[0026] (1) Preparation of N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one:

[0027] Dissolve 2.6 g of 3-nitro-1,2,4-triazol-5-one completely in 10 ml of acetone. At the same time, dissolve 5.34 g of N,N-dimethylaminomethylferrocene completely in 10 ml of acetone. Then slowly pour the N,N-dimethylaminomethylferrocene acetone solution into the 3-nitro-1,2,4-triazol-5-one acetone solution, stirring and mixing while pouring. Immediately, a yellow precipitate will form. After the precipitation is complete, filter and collect the yellow precipitate, and rinse it three times with ether. Then place it in a vacuum oven at 50 °C to dry and obtain the N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one compound powder; among them, the molar ratio of N,N-dimethylaminomethylferrocene to 3-nitro-1,2,4-triazol-5-one is 1.1;

[0028] (2) Preparation of graphene oxide suspension:

[0029] Disperse 0.2 g of graphene oxide in 15 ml of ultrapure water and exfoliate it in an ultrasonic bath at 200 W for 20 min to obtain a graphene oxide suspension;

[0030] (3) Preparation of graphene oxide-ferrocene suspension:

[0031] Take out 0.8 g of the N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one prepared in step (1) and place it in the graphene oxide suspension dispersed in step (2); place the mixture in an ultrasonic bath at 200 W for 20 min, and then place the above mixture in a magnetic stirrer for magnetic stirring for 20 min. After completion, obtain a graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one suspension;

[0032] (4) Preparation of graphene oxide-ferrocene composite:

[0033] Place the graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one suspension in step (3) in an ultrasonic bath at 200 W for 20 min to obtain a homogeneous mixture of graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one. Then quickly place the above mixture in a petri dish and freeze it into a block in an environment of -120 °C. Then place the above block in a freeze dryer for freeze-drying for 36 h to obtain a graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one composite with a graphene oxide content of 20%.

[0034] Characterization of graphene oxide-ferrocene composite

[0035] (1) Scanning electron microscope: See Figure 1

[0036] It can be seen from the electron microscope photos that the N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazole-5-one compound is re-complexed on the graphene oxide sheets and tightly wraps the graphene oxide. The graphene oxide provides a large number of active sites for the N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazole-5-one compound.

[0037] (2) Infrared spectrum: See Figure 2

[0038] According to the chemical structure of the graphene oxide-ferrocene composite, the corresponding relationship of the characteristic peaks in its spectrum can be inferred as: C=O is at 1643 cm -1 , N-O is at 1506 cm -1 and 1366 cm -1 , C-N is at 1300 cm -1 , C-H is at 1043 cm -1 . In addition, the characteristic absorption band of N-H is covered by the strong OH absorption band of water molecules in the KBr matrix, so it is not very obvious.

[0039] (3) Catalytic performance of the graphene oxide-ferrocene composite for AP: See Figure 3 and Table 1

[0040] The catalytic effect of graphene oxide, ferrocene composite and the prepared graphene oxide-ferrocene composite on the thermal decomposition of AP was characterized by a NETZSCH 214 type differential scanning calorimeter. Figure 3 is the DSC curves of the four samples at a heating rate of 10 °C / min, and Table 1 is the thermal decomposition data of the four samples. It can be seen from the thermal analysis results that: in terms of the decomposition peak temperature, graphene oxide and ferrocene composite reduce the low-temperature decomposition peak of AP by 14.9 and 1.6 °C respectively, and reduce its high-temperature decomposition peak by 64.4 and 99.2 °C respectively, while the introduction of the graphene oxide-ferrocene composite reduces the low- and high-temperature decomposition peaks of AP by 20.6 and 99.6 °C respectively. In terms of the heat release, the introduction of the graphene oxide-ferrocene composite increases the heat release of AP by 2808.3 J / g, which is much higher than the heat release of adding only the same mass of graphene oxide or ferrocene composite (2361.3 and 2004.3 J / g respectively). This shows that there is a synergistic effect between graphene oxide and ferrocene composite, making its catalytic effect on the thermal decomposition of AP stronger than the individual action of the two materials, indicating that the graphene oxide-ferrocene composite has excellent catalytic effect on AP.

[0041] Table 1 Thermal decomposition data of AP before and after mixing with graphene oxide, ferrocene composite and the prepared graphene oxide-ferrocene composite

[0042]

[0043] Embodiment 2:

[0044] (1) The preparation of N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one was the same as in Example 1;

[0045] (2) Preparation of graphene oxide suspension:

[0046] 0.4 g of graphene oxide was dispersed in 15 ml of ultrapure water and exfoliated under 200 W ultrasound for 20 min to obtain a graphene oxide suspension;

[0047] (3) Preparation of graphene oxide-ferrocene suspension:

[0048] 0.6 g of the N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazole-5-one prepared in step (1) is taken out and placed in the graphene oxide suspension dispersed in step (2); the mixed solution is dispersed in 200 W ultrasound for 20 min, and then the mixed solution is placed in a magnet for magnetic stirring for 20 min, after which a graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazole-5-one suspension is obtained;

[0049] (4) Preparation of graphene oxide-ferrocene complex:

[0050] The graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazole-5-one suspension in step (3) is dispersed in 200W ultrasound for 20 minutes to obtain a graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazole-5-one uniform mixture, and then the above mixture is quickly placed in a culture dish and placed in a -120°C environment to freeze into blocks, and then the above blocks are placed in a freeze dryer for freeze drying for 36 hours to obtain a graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazole-5-one complex with a graphene oxide content of 40%.

[0051] It should be noted that the present invention is not limited to the above-mentioned embodiments, and all variations that can be directly derived or associated with the contents disclosed by a person skilled in the art should be considered to be within the protection scope of the present invention.

Claims

1. A graphene oxide-ferrocene composite, characterized in that, The graphene oxide-ferrocene complex is a graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one complex; It includes the following steps: (1) Preparation of N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one: (2) Preparation of graphene oxide suspension: (3) Preparation of graphene oxide-ferrocene suspension: Place the prepared N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one in step (1) into the well-dispersed graphene oxide suspension in step (2); disperse the mixture in an ultrasonic bath for 20 min, and then place the above mixture on a magnetic stirrer for magnetic stirring for 20 min. After completion, a graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one suspension is obtained; (4) Preparation of graphene oxide-ferrocene complex: Disperse the graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one suspension in step (3) in an ultrasonic bath for 20 min to obtain a homogeneous mixture of graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one. Place the above mixture in a petri dish and freeze it into a block, and then place the above block in a freeze dryer. After complete drying, a graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one complex is obtained.

2. The synthesis method of the graphene oxide-ferrocene composite according to claim 1, characterized in that, The specific steps for preparing N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one are as follows: completely dissolve 3-nitro-1,2,4-triazol-5-one in acetone, and at the same time completely dissolve N,N-dimethylaminomethylferrocene in acetone. Then slowly pour the N,N-dimethylaminomethylferrocene acetone solution into the 3-nitro-1,2,4-triazol-5-one acetone solution, stirring and mixing while pouring. At this time, yellow precipitates should precipitate. After the precipitation is complete, filter and collect the yellow precipitate, and rinse it three times with ether. Then dry it in an oven to obtain the N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one compound powder.

3. The synthesis method of the graphene oxide-ferrocene composite according to claim 1, characterized in that, The specific preparation of graphene oxide suspension is as follows: disperse graphene oxide in ultrapure water and disperse it in an ultrasonic bath. After complete and uniform dispersion, a graphene oxide suspension is obtained.

4. The synthesis method of the graphene oxide-ferrocene composite according to claim 2, characterized in that, In step (1), the molar ratio of N,N-dimethylaminomethylferrocene to 3-nitro-1,2,4-triazol-5-one is 1.1-1.

2.

5. The synthesis method of the graphene oxide-ferrocene composite according to claim 2, characterized in that, In step (1), drying is carried out in an oven.

6. The synthesis method of the graphene oxide-ferrocene composite according to claim 1, wherein, In step (4), the specific drying time depends on the water content in the graphene oxide-N,N-dimethylaminomethylferrocene 3-nitro-1,2,4-triazol-5-one mixture.

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