A multimetallic hollow prussian blue analogue and a preparation method and application thereof
By employing a hierarchical synthesis method for multimetallic hollow Prussian blue analogues, the problem of structural collapse in Prussian blue analogues was solved, achieving highly efficient and stable catalytic decomposition of ammonium perchlorate and improving the performance of solid propellants.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WUHAN UNIV
- Filing Date
- 2024-01-19
- Publication Date
- 2026-07-31
AI Technical Summary
Existing Prussian blue analogues suffer from structural collapse during the catalytic decomposition of ammonium perchlorate, affecting their sustained catalytic ability and making it difficult to achieve efficient and stable catalytic effects.
A hierarchical multimetallic hollow Prussian blue analogue was synthesized via fractional synthesis and self-template sacrificial method to form a thermally stable hollow structure for catalytic decomposition of ammonium perchlorate.
It significantly improved the thermal decomposition behavior of ammonium perchlorate, reduced the decomposition temperature, and maintained the structural stability of the catalyst, achieving a highly efficient and sustained catalytic effect.
Smart Images
Figure CN118145678B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of solid rocket propellant technology, and in particular to a multimetallic hollow Prussian blue analogue, its preparation method, and its application. Background Technology
[0002] Solid rocket engines, with their advantages of simple structure, high reliability, easy mobile deployment, and rapid response, have become the main power source for strategic and tactical weapons. As a crucial power source for missiles and special operations engines, the combustion behavior of solid propellants, particularly the oxidizer, significantly impacts the actual combat capability of missiles.
[0003] Ammonium perchlorate (AP) is currently the most common oxidizer in composite solid propellants, and its thermal decomposition behavior determines the overall performance of the final composite solid propellant. Adding a catalyst to achieve efficient AP decomposition is considered an effective method. Currently, Prussian blue analogues (PBA) have been shown to have good catalytic activity, with improvements in key parameters measuring AP thermal decomposition behavior, such as low-temperature decomposition peak and high-temperature decomposition peak. However, researchers have not yet been able to further refine the regulation of catalytic behavior, especially as the structural collapse of hollow PBA during catalysis affects its sustained catalytic capacity. Therefore, overcoming the bottleneck of PBA in AP catalyst thermal decomposition, particularly through ingenious structural design and optimized synthesis methods to obtain thermally stable hollow PBA to achieve efficient and sustained catalytic effects, is crucial for improving the overall burning rate. Summary of the Invention
[0004] Based on the above, this invention proposes the idea of achieving optimal catalytic performance through the design of a stable bonded structure. The establishment of a stable bonded hollow structure is beneficial to the stability, sustainability, and efficiency of the catalytic process. The multi-metallic element composition can further enhance the overall catalytic efficiency, significantly improve the thermal decomposition behavior of AP, further enhance the performance of solid propellants, and increase specific impulse and power. Simultaneously, this invention employs a fractional synthesis method, i.e., the establishment of a hierarchical structure combined with a self-template sacrifice method, to synthesize the hollow structure. The gradient design in the synthesis greatly enhances the stability of the formed hollow structure, resulting in a hollow structure with extremely high thermal stability.
[0005] To achieve the above objectives, the present invention adopts the following technical solution:
[0006] A method for preparing a multimetallic hollow Prussian blue analogue includes the following steps:
[0007] S1. Dissolve the metal salt in a solvent and a polyol, and stir until a uniform and transparent metal precursor solution is formed;
[0008] S2. The metal precursor solution prepared in S1 is heated through a reaction vessel to obtain a metal alkoxide.
[0009] S3. Disperse the metal alkoxide prepared in S2 into ethanol. After dispersion, add it dropwise into a hexacyanide salt solution and heat it to react, thus obtaining a multimetallic hollow Prussian blue analog.
[0010] S4. The Prussian blue analog prepared in S3 is washed multiple times to remove impurities, and then dried to obtain the purified multimetallic hollow Prussian blue analog.
[0011] In a preferred embodiment of a method for preparing a multimetallic hollow Prussian blue analogue, in step S1, the metal salt includes one or more of nitrate, perchlorate, hydrochloride, acetate, and sulfate, and the total content of the metal salt is 4-10 mmol.
[0012] In a preferred embodiment of a method for preparing a multimetallic hollow Prussian blue analogue, in step S1, the solvent includes one of methanol, ethanol, propanol, isopropanol, and tert-butanol, and the volume of the solvent is 20-50 mL.
[0013] In a preferred embodiment of a method for preparing a polymetallic hollow Prussian blue analogue, in step S1, the polyol includes any one of propylene glycol, glycerol, butanediol, and glycerol, the volume of the polyol is 4-10 mL, and the ratio of the polyol to the metal salt is 1 mL: (0.8-1.2 mmol).
[0014] In a preferred embodiment of a method for preparing a multimetallic hollow Prussian blue analogue, in step S3, the hexacyanate salt comprises one of potassium hexacyanoferrate, sodium hexacyanoferrate, potassium hexacyanoferrousate, sodium hexacyanoferrousate, potassium hexacyanocobalaminate, and sodium hexacyanocobalaminate, the volume of the hexacyanate salt solution is 100 mL, and the mass ratio of the hexacyanate salt to the metal alkoxide is (1-5):1.
[0015] In a preferred embodiment of a method for preparing a multimetallic hollow Prussian blue analogue, in step S3, the content of the metal alkoxide is 100-600 mg, and the volume of the ethanol is 100-200 ml.
[0016] In a preferred embodiment of a method for preparing a polymetallic hollow Prussian blue analogue, in step S2, the heating time is 3-10 h and the heating temperature is 100-200 °C; in step S3, the heating temperature is 50-120 °C and the heating time is 3-10 h; and in step S4, the drying temperature is 70-110 °C and the drying time is 1-72 h.
[0017] A multimetallic hollow Prussian blue analogue, prepared by any one of the preparation methods described above.
[0018] As a preferred embodiment of a multimetallic hollow Prussian blue analogue, the molecular formula of the multimetallic hollow Prussian blue analogue is AxMy[M'z(CN)6], wherein A includes one or two of Na and K, M includes one or more of Fe, Co, Ni, Cu, Zn, and Mn, and M' includes any one or two of Fe and Co.
[0019] As a preferred embodiment of the application of a multimetallic hollow Prussian blue analogue, the multimetallic hollow Prussian blue analogue is added to a solid propellant as a catalyst for the decomposition of ammonium perchlorate, wherein the amount of the multimetallic hollow Prussian blue analogue is 5 wt% or less of the total mass of the ammonium perchlorate.
[0020] The beneficial effects of this invention are as follows:
[0021] This invention applies a multi-metallic hollow Prussian blue analogue with good thermal stability to solid propellants. Its unique hierarchical stabilizing structure can significantly regulate the adsorption and diffusion behavior of gases during the thermal decomposition of AP, thereby affecting the low-temperature and high-temperature decomposition behavior of AP. Compared with existing metal oxide and metal-organic framework catalysts, it can achieve better catalytic efficiency.
[0022] Therefore, multi-metallic hollow Prussian blue analogues with good thermal stability have excellent catalytic effects on the thermal decomposition of AP when applied to solid propellants. Their catalytic effect can significantly reduce the decomposition temperature of AP. At the same time, due to the establishment of hierarchical structure and the self-template sacrifice synthesis method, the catalyst can still maintain its original structure after decomposition and has good thermal stability, thus making the overall catalytic effect continuous and efficient. Attached Figure Description
[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments of the present invention will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the content of the embodiments of the present invention and these drawings without creative effort.
[0024] Figure 1 XRD patterns of the metal alkoxide and multimetal hollow Prussian blue analog powder prepared in Example 7;
[0025] Figure 2 SEM and TEM images of the metal alkoxides and multimetallic hollow Prussian blue analogs prepared in Example 3;
[0026] Figure 3 This is a SEM image of AP catalyzed by the multimetallic hollow Prussian blue analog prepared in Example 4;
[0027] Figure 4 Differential scanning calorimetry (DSC) curves for the pure AP decomposition process;
[0028] Figure 5 Differential scanning calorimetry (DSC) curves of AP decomposition catalyzed by the multimetallic hollow Prussian blue analogue prepared in Example 4;
[0029] Figure 6 The DSC curves of AP catalyzed by Prussian blue analog thermal decomposition catalysts prepared by the commonly used coprecipitation method (taking CoFe-PBA as an example). Detailed Implementation
[0030] To facilitate understanding of the present invention, a more comprehensive description will be provided below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention. Unless otherwise defined, all technical and scientific terms used in this invention pertain to the technical field of the invention.
[0031] The present invention will be further described below through specific embodiments.
[0032] Example 1
[0033] A method for preparing a multimetallic hollow Prussian blue analogue specifically includes the following steps:
[0034] S1. Preparation of metal precursor solution: First, dissolve 4 mmol of nickel sulfate in 30 mL of ethanol and 4 mL of propylene glycol, stirring until a homogeneous and transparent solution is formed.
[0035] S2. Synthesis of metal alkoxides: The metal precursor solution is heated to a certain temperature of 100℃ in a reaction vessel, and the total heating time is controlled within 10 hours to obtain the metal alkoxide.
[0036] S3, Preparation of Prussian blue analogues: 100 mg of the prepared metal alkoxide was dispersed in 100 ml of ethanol. After dispersion, it was added dropwise to 100 mL of potassium hexacyanoferroate solution containing 100 mg. The reaction was heated to 50 °C and continued for 8 h.
[0037] S4. Purification of Prussian blue analogues: After the reaction, the Prussian blue analogues were washed repeatedly with deionized water and ethanol to remove impurities. The purified Prussian blue analogues were placed in a drying oven at 110°C for 1 hour to obtain nickel-Prussian blue hollow spheres (Ni-HSs) assembled from Prussian blue cubes formed by Ni-Fe.
[0038] Example 2
[0039] A method for preparing a multimetallic hollow Prussian blue analogue specifically includes the following steps:
[0040] S1. Preparation of metal precursor solution: First, dissolve 3 mmol of copper perchlorate and 3 mmol of manganese chloride in 50 mL of methanol and 5 mL of butanediol, stirring until a homogeneous and transparent solution is formed.
[0041] S2. Synthesis of metal alkoxides: The metal precursor solution is heated to a certain temperature of 120℃ in a reaction vessel, and the total heating time is controlled at 8h to obtain the metal alkoxide.
[0042] S3, Preparation of Prussian blue analogues: 200 mg of the prepared metal alkoxide was dispersed in 120 ml of ethanol. After dispersion, it was added dropwise to 100 mL of sodium hexacyanoferrate solution containing 0.4 g. The reaction was heated to 50 °C and continued for 10 h.
[0043] S4. Purification of Prussian blue analogues: After the reaction, the Prussian blue analogues were washed repeatedly with deionized water and ethanol to remove impurities. The purified Prussian blue analogues were placed in a 90°C drying oven for 12 hours to obtain manganese copper Prussian blue hollow spheres (MnCu-HSs) assembled from Prussian blue cubes formed by Mn-Cu-Fe.
[0044] Example 3
[0045] A method for preparing a multimetallic hollow Prussian blue analogue specifically includes the following steps:
[0046] S1. Preparation of metal precursor solution: First, dissolve 5 mmol of zinc nitrate and 5 mmol of copper sulfate in 50 mL of isopropanol and 10 mL of glycerol, stirring until a homogeneous and transparent solution is formed.
[0047] S2. Synthesis of metal alkoxides: The metal precursor solution is heated to a certain temperature of 140℃ in a reaction vessel, and the total heating time is controlled at 9h to obtain metal alkoxides.
[0048] S3, Preparation of Prussian blue analogues: 400 mg of the prepared metal alkoxide was dispersed in 160 ml of ethanol. After dispersion, it was added dropwise to 100 mL of potassium hexacyanoferrate solution containing 1.2 g. The reaction was heated to 120 °C and continued for 3 h.
[0049] S4. Purification of Prussian blue analogues: After the reaction, the Prussian blue analogues were washed repeatedly with deionized water and ethanol to remove impurities. The purified Prussian blue analogues were placed in a 90℃ drying oven for 12 hours to obtain copper-zinc Prussian blue hollow spheres (CuZn-HSs) assembled from Prussian blue cubes formed by Cu-Zn-Fe.
[0050] Example 4
[0051] A method for preparing a multimetallic hollow Prussian blue analogue specifically includes the following steps:
[0052] S1. Preparation of metal precursor solution: First, dissolve 7 mmol of cobalt nitrate in 40 mL of isopropanol and 8 mL of glycerol, stirring until a homogeneous and transparent solution is formed.
[0053] S2. Synthesis of metal alkoxides: The metal precursor solution is heated to a certain temperature of 180℃ in a reaction vessel, and the total heating time is controlled at 6h to obtain the metal alkoxide.
[0054] S3, Preparation of Prussian blue analogues: 300 mg of the prepared metal alkoxide was dispersed in 140 ml of ethanol. After dispersion, it was added dropwise to 100 mL of potassium hexacyanoferroate solution containing 0.9 g. The reaction was heated to 90 °C and continued for 5 h.
[0055] S4. Purification of Prussian blue analogues: After the reaction, the Prussian blue analogues were washed repeatedly with deionized water and ethanol to remove impurities. The purified Prussian blue analogues were placed in a 90°C drying oven for 12 hours to obtain cobalt Prussian blue hollow spheres (Co-HSs) assembled from Prussian blue cubes formed by Co-Fe.
[0056] Example 5
[0057] A method for preparing a multimetallic hollow Prussian blue analogue specifically includes the following steps:
[0058] S1. Preparation of metal precursor solution: First, dissolve 2 mmol copper sulfate + 2 mmol cobalt chloride + 2 mmol manganese nitrate + 2 mmol nickel chloride in 50 ml tert-butanol and 10 ml glycerol, stirring until a homogeneous and transparent solution is formed.
[0059] S2. Synthesis of metal alkoxides: The metal precursor solution is heated to a certain temperature of 200℃ in a reaction vessel, and the total heating time is controlled at 3h to obtain the metal alkoxide.
[0060] S3, Preparation of Prussian blue analogues: 500 mg of the prepared metal alkoxide was dispersed in 180 ml of ethanol. After dispersion, it was added dropwise to 100 mL of potassium hexacyanocobaltate solution containing 2 g. The reaction was heated to 110 °C and continued for 7 h.
[0061] S4. Purification of Prussian blue analogues: After the reaction, the Prussian blue analogues were washed repeatedly with deionized water and ethanol to remove impurities. The purified Prussian blue analogues were placed in a 90°C drying oven for 12 hours to obtain hollow Prussian blue spheres (MnCoNiCu-HSs) assembled from Prussian blue cubes formed by Mn-Co-Ni-Cu.
[0062] Example 6
[0063] A method for preparing a multimetallic hollow Prussian blue analogue specifically includes the following steps:
[0064] S1. Preparation of metal precursor solution: First, dissolve 2 mmol nickel nitrate + 3 mmol copper nitrate in 30 ml isopropanol and 6 ml butanediol, stirring until a homogeneous and transparent solution is formed.
[0065] S2. Synthesis of metal alkoxides: The metal precursor solution is heated to a certain temperature of 160℃ in a reaction vessel, and the total heating time is controlled at 6h to obtain the metal alkoxide.
[0066] S3, Preparation of Prussian blue analogues: 600 mg of the prepared metal alkoxide was dispersed in 200 ml of ethanol. After dispersion, it was added dropwise to 100 mL of sodium hexacyanocobaltate solution containing 3 g. The reaction was heated to 70 °C and continued for 10 h.
[0067] S4. Purification of Prussian blue analogues: After the reaction, the Prussian blue analogues were washed repeatedly with deionized water and ethanol to remove impurities. The purified Prussian blue analogues were then placed in an 80℃ drying oven for 45 hours to form Co-Ni-Cu nickel-copper Prussian blue hollow spheres (NiCu-HSs).
[0068] Example 7
[0069] A method for preparing a multimetallic hollow Prussian blue analogue specifically includes the following steps:
[0070] S1. Preparation of metal precursor solution: First, dissolve 2 mmol cobalt acetate + 4 mmol ferric acetate in 20 mL propanol and 7 mL propylene glycol, stirring until a homogeneous and transparent solution is formed.
[0071] S2. Synthesis of metal alkoxides: The metal precursor solution is heated to a certain temperature of 150℃ in a reaction vessel, and the total heating time is controlled at 6h to obtain the metal alkoxide.
[0072] S3, Preparation of Prussian blue analogues: 200 mg of the prepared metal alkoxide was dispersed in 120 ml of ethanol. After dispersion, it was added dropwise to 100 mL of sodium hexacyanoferroate solution containing 0.6 g. The reaction was heated to 100 °C and continued for 3 h.
[0073] S4. Purification of Prussian blue analogues: After the reaction, the Prussian blue analogues were washed repeatedly with deionized water and ethanol to remove impurities. The purified Prussian blue analogues were placed in a drying oven at 70°C for 72 hours to obtain iron-cobalt Prussian blue hollow spheres (FeCo-HSs) assembled from Prussian blue cubes formed by Fe-Co-Fe.
[0074] The polymetallic hollow Prussian blue analog prepared in the above examples was used to catalyze the decomposition of ammonium perchlorate, wherein the amount of polymetallic hollow Prussian blue analog added to ammonium perchlorate was 1-5% of the total mass of ammonium perchlorate.
[0075] To further illustrate the key points of this patent, a commonly used ammonium perchlorate thermal decomposition catalyst (Prussian blue analogue) will be used as a comparative example, specifically CoFe-PBA.
[0076] Figure 1 The XRD results are shown for the metal alkoxides and multimetallic hollow Prussian blue (PBA) powders prepared in Example 7. The comparison revealed that the broad peak around 12° corresponds well to the metal alkoxides in the standard spectrum, and the prepared PBAs all correspond to the standard cards (taking FeCo-HSs as an example).
[0077] Figure 2 The metal alkoxide and the multimetallic hollow Prussian blue analog powder prepared in Example 3 were subjected to SEM and TEM tests. It can be clearly seen that the metal alkoxide is a solid smooth sphere, while the prepared CuZn-HSs is a hollow spherical shell assembly structure.
[0078] Figure 3 The image shows the SEM image of the multimetallic Prussian blue analog prepared in Example 4 after AP catalysis. The original structure was maintained after AP catalysis, and no structural collapse was observed, indicating good thermal stability.
[0079] Figure 4 The differential scanning calorimetry (DSC) curves for the pure AP decomposition process show two distinct stages at a heating rate of 10 °C / min, generally referred to as the low-temperature decomposition stage and the high-temperature decomposition stage. The peak temperature of the high-temperature decomposition stage is 414.1 °C.
[0080] Figure 5 The differential scanning calorimetry (DSC) curve of the AP decomposition process catalyzed by Co-HSs prepared in Example 4 shows that the entire decomposition stage is a continuous process with a peak value of 292.5℃ at a heating rate of 10℃ / min.
[0081] Will Figure 4 and Figure 5 By comparison, it can be seen that the addition of Co-HSs makes the original staged decomposition process into a complete and continuous process and greatly reduces the decomposition temperature. The peak temperature of the high-temperature decomposition stage changes from 414.1℃ to 292.5℃, which shows good catalytic performance.
[0082] Figure 6 The image shows the DSC curves of AP catalyzed by commonly used AP thermal decomposition catalysts (Prussian blue analogues). Taking CoFe-PBA as an example, it can reduce the high-temperature decomposition peak of AP to 312.2℃, which is significantly lower than that of Co-HSs.
[0083] Therefore, the multimetallic hollow Prussian blue analogue prepared in this application has excellent catalytic effect on the decomposition of ammonium perchlorate. Its catalytic effect can significantly reduce the decomposition temperature of AP, and the catalyst can still maintain its original structure after decomposition, exhibiting good thermal stability.
[0084] Note that the above description is merely a preferred embodiment of the present invention and the technical principles employed. Those skilled in the art will understand that the present invention is not limited to the specific embodiments described herein, and various obvious changes, readjustments, and substitutions can be made without departing from the scope of protection of the present invention. Therefore, although the present invention has been described in detail through the above embodiments, the present invention is not limited to the above embodiments, and may include many other equivalent embodiments without departing from the concept of the present invention, the scope of which is determined by the scope of the appended claims.
Claims
1. A method for preparing a multimetallic hollow Prussian blue analogue, characterized in that, Includes the following steps: S1. Dissolve the metal salt in a solvent and a polyol, and stir until a uniform and transparent metal precursor solution is formed; the metal ions in the metal salt include one or more of Fe, Co, Ni, Cu, Zn, and Mn; S2. The metal precursor solution prepared in S1 is heated through a reaction vessel to obtain a metal alkoxide. S3. Disperse the metal alkoxide prepared in S2 into ethanol. After dispersion, add it dropwise to a hexacyanate salt solution and heat to react, thereby obtaining a multimetallic hollow Prussian blue analogue. The hexacyanate salt includes one of potassium hexacyanoferrate, sodium hexacyanoferrate, potassium hexacyanoferrousate, sodium hexacyanoferrousate, potassium hexacyanocobalaminate, and sodium hexacyanocobalaminate. S4. The Prussian blue analog prepared in S3 is washed multiple times to remove impurities, and then dried to obtain the purified multimetallic hollow Prussian blue analog.
2. The method for preparing the multimetallic hollow Prussian blue analogue according to claim 1, characterized in that, In S1, the metal salt includes one or more of nitrate, perchlorate, hydrochloride, acetate, and sulfate, and the total content of the metal salt is 4-10 mmol.
3. The method for preparing the multimetallic hollow Prussian blue analogue according to claim 1, characterized in that, In step S1, the solvent includes one of methanol, ethanol, propanol, isopropanol, and tert-butanol, and the volume of the solvent is 20-50 mL.
4. The method for preparing the multimetallic hollow Prussian blue analogue according to claim 1, characterized in that, In S1, the polyol includes one of propylene glycol, glycerol, butanediol, and glycerol, the volume of the polyol is 4-10 mL, and the ratio of the polyol to the metal salt is 1 mL: (0.8-1.2 mmol).
5. The method for preparing the multimetallic hollow Prussian blue analogue according to claim 1, characterized in that, In step S3, the volume of the hexacyanate solution is 100 mL, and the mass ratio of the hexacyanate to the metal alkoxide is (1-5):
1.
6. The method for preparing the multimetallic hollow Prussian blue analogue according to claim 1, characterized in that, In step S3, the content of the metal alkoxide is 100-600 mg, and the volume of the ethanol is 100-200 ml.
7. The method for preparing the multimetallic hollow Prussian blue analogue according to claim 1, characterized in that, In step S2, the heating time is 3-10 h and the heating temperature is 100-200 ℃; in step S3, the heating temperature is 50-120 ℃ and the heating time is 3-10 h; in step S4, the drying temperature is 70-110 ℃ and the drying time is 1-72 h.
8. A multimetallic hollow Prussian blue analogue, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.
9. A multimetallic hollow Prussian blue analogue according to claim 8, characterized in that, The molecular formula of the multi-metal hollow Prussian blue analogue is A x M y [M ’ z (CN)6], wherein A includes one or both of Na and K, M includes one or more of Fe, Co, Ni, Cu, Zn, and Mn, M ’ includes one or both of Fe and Co.
10. The application of a multimetallic hollow Prussian blue analogue according to claim 9, characterized in that, The multimetallic hollow Prussian blue analogue is added to the solid propellant as a catalyst for the decomposition of ammonium perchlorate, and the amount of the multimetallic hollow Prussian blue analogue is 5 wt% or less of the total mass of the ammonium perchlorate.