Trinuclear ferrocene-based metal composite material as well as preparation method and application thereof

Abstract

The invention discloses a trinuclear ferrocene-based metal composite material and a preparation method and application thereof, and belongs to the field of burning rate catalysts.The preparation method comprises the steps that ferrocenyl acetaldehyde and ferrocenyl dihydrazone are dissolved, then heating reflux is conducted, purification treatment is conducted, a trinuclear ferrocene ligand is prepared, the trinuclear ferrocene ligand is dissolved in a solvent, a mixed solution A is prepared, and the mixed solution B is prepared; dividing the mixed solution A into three equal parts, and respectively adding a Co salt solution, a Fe salt solution and a mixed solution of Co salt and Fe salt to respectively prepare the trinuclear ferrocene-based metal composite materials of Fc3N4 / Co, Fc3N4 / Fe and Fc3N4 / CoFe. The technical problem that a burning rate catalyst prepared by an existing preparation method is not high in pyrolysis catalytic performance on ammonium perchlorate is solved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of burning rate catalysts, and particularly relates to a trinuclear ferrocene-based metal composite material and a preparation method and application thereof. BACKGROUND

[0002] Composite solid propellants (CSPs) are a kind of key power source, and are widely used in control systems, missile propellants, pressure generators for deep sea operations, and gas generators for airbags in the aerospace field due to their excellent combustion performance. Ammonium perchlorate (AP) is a kind of vital oxidizer, and is widely used in CSPs due to its large gas production, high oxygen content, and good compatibility with other solid propellant components. In composite solid propellants, the mass ratio of AP is as high as 60%-80%, and plays a decisive role in the combustion performance of solid propellants. However, pure AP has some problems, such as high decomposition temperature, high apparent activation energy, and low heat release in the high-temperature decomposition stage (HTD), which seriously restricts the combustion performance of solid propellants based on AP. Therefore, developing efficient catalysts to improve the pyrolysis performance of AP has become a safe and effective solution. Adding an appropriate amount of burning rate catalyst can reduce the HTD decomposition temperature and activation energy of AP, increase the heat release of AP, and thus significantly improve the combustion performance of propellants based on AP.

[0003] Among current burning rate catalysts, ferrocene and its derivatives are widely used due to their excellent electron transfer ability and thermal stability, but traditional alkyl ferrocenes (such as butyl ferrocene and catocene) have the defects of low molecular weight and easy migration and volatilization, which leads to storage failure and safety hazards. Ferrocene-based polymers can form a crosslinked network structure with propellants and binders during the curing reaction, but introduce a large amount of C and H elements, which reduces their catalytic activity for AP decomposition and heat release, thus limiting their application in CSPs.

[0004] Chinese patent CN117923992A discloses a preparation method and application method of a ferrocene guanidine type burning rate catalyst. Ferrocene formaldehyde and triaminoguanidine are used as raw materials to synthesize a reactive ferrocene-based guanidine ligand; the reactive ferrocene-based guanidine ligand is mixed with a first metal salt containing Co 2+ to obtain a first metal salt mixture; and the first metal salt mixture is mixed with a second metal salt containing Cu 2+ , Zn 2+ , and Mn 2+The second metal salt is subjected to a complex reaction to obtain three ferrocene guanidine bimetallic derivatives, namely three catalysts capable of ammonium perchlorate pyrolysis, the prepared ferrocene guanidine burning rate catalyst has the characteristics of high efficiency, high energy and migration resistance, and the raw material source is wide and the preparation process is simple, but the catalyst prepared by the preparation method cannot accurately cut off the N-H and Cl-O bonds, resulting in low catalytic performance for ammonium perchlorate pyrolysis. SUMMARY

[0005] In order to overcome the shortcomings of the prior art, the purpose of the present application is to provide a trinuclear ferrocene metal composite material and a preparation method and application thereof, so as to solve the technical problem of low catalytic performance of the burning rate catalyst prepared by the existing preparation method for ammonium perchlorate pyrolysis.

[0006] In order to achieve the above purpose, the technical scheme is adopted as follows: The present application provides a preparation method of a trinuclear ferrocene metal composite material, comprising the following steps: 1) Dissolve ferrocene acetaldehyde and ferrocene-based bishydrazones, heat and reflux, and purify to obtain a trinuclear ferrocene ligand Fc3N4; 2) Dissolve the trinuclear ferrocene ligand Fc3N4 in a solvent to prepare a mixed solution A with a concentration of (0.1-0.2) mol / L; 3) Divide the mixed solution A into three equal parts, and add Co salt solution, Fe salt solution and mixed solution of Co salt and Fe salt respectively to prepare Fc3N4 / Co, Fc3N4 / Fe and Fc3N4 / CoFe trinuclear ferrocene metal composite materials.

[0007] Preferably, in step 1), the molar ratio of ferrocene acetaldehyde and ferrocene-based bishydrazones is (1-2):(0.5-1); in step 3), the molar ratio of Co salt and Fe salt in the mixed solution is 1:1; the amount relationship between the mixed solution A and the mixed solution of Co salt and Fe salt is that 1 mmol of trinuclear ferrocene ligand Fc3N4 corresponds to 1 mmol of Co salt and 1 mmol of Fe salt; the amount relationship between the mixed solution A and the Co salt solution is that 1 mmol of trinuclear ferrocene ligand Fc3N4 corresponds to 1 mmol of Co salt; the amount relationship between the mixed solution A and the Fe salt solution is that 1 mmol of trinuclear ferrocene ligand Fc3N4 corresponds to 1 mmol of Fe salt.

[0008] In the above step 3), the mixed solution A is divided into three parts, which are mixed solution A1, mixed solution A2 and mixed solution A3: The mixed solution A1 is added to the mixed solution of Co salt and Fe salt, and after reaction, the trinuclear ferrocene metal composite Fc3N4 / CoFe is prepared; the mixed solution A2 is added to the Co salt solution, and after reaction, the trinuclear ferrocene metal composite Fc3N4 / Co is prepared; the mixed solution A3 is added to the Fe salt solution, and after reaction, the trinuclear ferrocene metal composite Fc3N4 / Fe is prepared.

[0009] Further preferably, in step 1), the ferrocene acetaldehyde and the ferrocenyl bis-hydrazone are dissolved in ethanol.

[0010] Further preferably, in step 2), the trinuclear ferrocene ligand Fc3N4 is dissolved in dimethyl sulfoxide.

[0011] Preferably, in step 3), the Co salt in the Co salt solution is Co(NO3)2·6H2O, the Fe salt in the Fe salt solution is Fe(NO3)2·3H2O; the Co salt in the mixed solution of Co salt and Fe salt is Co(NO3)2·6H2O, and the Fe salt is Fe(NO3)2·3H2O.

[0012] Preferably, in step 1), the heating temperature is 70-80℃, and the reaction time is 5-8h.

[0013] Preferably, the purification treatment comprises a solvent evaporation under reduced pressure process and a recrystallization process; in the solvent evaporation under reduced pressure process, in step 1), the temperature is 100-120℃, and the vacuum degree is 1x10-1x10 2 Pa; in the recrystallization process, ethanol and water are used as the mixed solvent, and the volume ratio of ethanol to water is 1:1.

[0014] Preferably, in step 2), the mixed solution A is subjected to heating, cooling, centrifugation, washing and drying treatment.

[0015] Preferably, the heating temperature is 110-130℃, and the reaction time is 11-13h.

[0016] Preferably, ethanol and distilled water are used for alternate washing.

[0017] Further preferably, ethanol and distilled water are used for alternate washing for 3 times.

[0018] Preferably, the centrifugation condition is: the rotation speed is 2000-4000rpm, and the time is 5-15min.

[0019] The application also provides a trinuclear ferrocene metal composite prepared by the preparation method of the trinuclear ferrocene metal composite.

[0020] The application also provides application of the trinuclear ferrocene metal composite in pyrolysis of ammonium perchlorate.

[0021] Compared with the prior art, the present application has the following beneficial effects: The present application provides a preparation method of a trinuclear ferrocene metal composite material, which uses ferrocene acetaldehyde and ferrocene-based bis-hydrazone as raw materials, synthesizes a novel trinuclear ferrocene ligand first, and then selects Co 2+ and Fe 2+ as metal nodes to complex with the ligand, respectively, to obtain a trinuclear ferrocene metal composite material of Fc3N4 / CoFe, Fc3N4 / Co or Fc3N4 / Fe, the aldehyde group (-CHO) of the ferrocene acetaldehyde (Fc-CHO) raw material and the hydrazone group (-NH-NH2) of the ferrocene-based bis-hydrazone (Fc-NH-NH2) undergo a dehydration condensation reaction to form a new C=N double bond (imine bond, also known as hydrazone bond), thereby covalently connecting two ferrocene units, since the ferrocene-based bis-hydrazone molecule itself already contains two ferrocene units (Fc-) and has two reaction sites (-NH-NH2), and the ferrocene acetaldehyde provides one ferrocene unit and one reaction site (-CHO). By accurately controlling the dosage ratio and molar ratio, one ferrocene-based bis-hydrazone molecule can react with two ferrocene acetaldehyde molecules, and finally form a symmetrical, covalently connected organic macromolecular ligand of three ferrocene (Fc) units, i.e. three ferrocene nuclei are covalently fixed on the same organic molecular skeleton, not only providing a high density of catalytically active centers (ferrocene groups), but also effectively avoiding the volatilization and loss of the catalyst, ensuring the continuity and stability of the catalytic effect during the entire decomposition process of AP, thereby promoting the stable and complete combustion of AP. At the same time, a molar ratio of (1-2) mmol:(0.5-1) mmol ensures that the aldehyde group and the hydrazone group react in close to the optimal stoichiometry, maximizing the target ligand yield and reducing by-products. The introduction of Co and Fe elements in a 1:1 molar ratio provides the possibility of forming a bimetallic synergistic catalytic center, making the CoFe bimetallic system have more superior catalytic performance than a single metal.

[0022] The composite material is based on a composite material of a multi-nuclear ferrocene electron relay and a bimetallic synergistic catalytic center, and forms a rigid network structure through the trinuclear ferrocene and the metal nodes, and due to the synergistic catalytic effect of the transition metal nodes and the ferrocene-based ligands in the structure, as well as the diversified chemical composition, large surface area and excellent thermal stability, the metal composite material has the effects of enhanced catalysis and anti-migration, and the molecular weight is significantly improved compared with traditional ferrocene derivatives. Further, the molar ratio of ferrocenyl aldehyde and ferrocenyl bis-hydrazone is (1-2):(0.5-1), which ensures that the reactant molecules can react according to the designed path. The ferrocenyl bis-hydrazone molecule has two hydrazone groups (-NHNH2), and each hydrazone group needs to react with an aldehyde group (-CHO) of ferrocenyl aldehyde. This ratio range can ensure that both hydrazone groups can fully react to efficiently generate the target trinuclear ligand Fc3N4; The amount of mixed solution A and the Co salt solution, the Fe salt solution, and the mixed solution of Co salt and Fe salt is 1 mmol of Co salt, Fe salt, and Co salt and Fe salt per 1 mmol of Fc3N4, which ensures that each batch of prepared composite material has the same metal-ligand ratio, thereby ensuring that its chemical structure and catalytic activity are uniform, stable, and reproducible; The molar ratio of Co salt and Fe salt in the mixed solution is 1:1, which ensures that in the final composite material, Co and Fe atoms can be arranged adjacent to each other in the most compact and uniform manner, providing a structural basis for the maximization of this synergistic effect. It also helps to form a well-defined Co-Fe binuclear active center, rather than random Co or Fe clusters.

[0023] Further, nitrate salts generally have good solubility in polar protic solvents (such as water) and polar aprotic solvents (such as DMSO), which ensures that metal ions can fully and uniformly contact and react with the ligand Fc3N4, which is conducive to the formation of uniform composite materials. Nitrate salts are easily decomposed into corresponding metal oxides during subsequent heating and vacuum drying, which helps to form metal oxides with high catalytic activity in the composite material, thereby optimizing the catalytic performance of the metal composite material.

[0024] Further, heating and refluxing is a key step in the synthesis of the ligand. The temperature range of 70-80°C is higher than the boiling point of ethanol (78°C), which ensures that the reaction is carried out under reflux conditions, providing sufficient energy to overcome the activation energy of the reaction, accelerating molecular collisions and reaction rates. At the same time, this temperature is a mild condition that can effectively prevent the decomposition or side reactions of the ferrocenyl group or newly formed hydrazone bond (C=N), protecting the integrity of the catalytically active center. The reaction time of 5-8 h ensures that the reaction has enough time to proceed completely, so that the raw materials can be converted into the target product as much as possible, improving the yield and purity of the product.

[0025] Further, the conditions of high temperature and high vacuum (100-120°C, 10-100 Pa) can quickly and completely evaporate low-boiling-point solvents (ethanol) and unreacted volatile raw materials, avoiding their entry into subsequent steps as impurities. Compared with normal pressure distillation, this condition greatly reduces the operating temperature, effectively preventing the decomposition, oxidation, or structural changes of the ferrocenyl group in thermosensitive compounds at high temperature for a long time, ensuring the structural integrity of the ligand molecules.

[0026] Further, ethanol ensures that the mixed solvent has sufficient capacity to completely dissolve the target product Fc3N4 in the crude product when heated, avoiding product loss due to incomplete dissolution. Water ensures that the solubility of Fc3N4 can be significantly reduced when cooled. The 1:1 ratio provides a sufficiently low polarity to enable Fc3N4 to be analyzed when cooled, while maintaining a sufficiently high solubility to completely dissolve Fc3N4 when heated.

[0027] Further, dimethyl sulfoxide (DMSO) is a polar aprotic solvent with good solubility, which can effectively dissolve organic ligands and metal salts to provide an environment for homogeneous reaction, ensuring that the ligand and metal ion are uniformly and fully coordinated to form a complex material with uniform structure. The dosage ratio of 1 mmol:30 mL controls the reaction concentration, which ensures sufficient collision opportunities between molecules for coordination, while avoiding excessive concentration leading to premature precipitation of the product, inclusion of impurities, or formation of amorphous aggregates.

[0028] Further, the heating conditions of 110-130°C and 11-13h can promote the formation of more stable complex materials between the ligand and metal ion, optimizing the stability of the material.

[0029] Further, water can dissolve and wash away inorganic salt byproducts (such as NO3 - ); ethanol can wash away organic small molecule impurities and residual DMSO. Alternating washing can most thoroughly clean the material surface, exposing more active sites and preventing impurities from blocking the pores or covering the active centers.

[0030] The application also provides applications of the above-mentioned trinuclear ferrocene-based metal composite material: applying the composite material to AP pyrolysis, through the synergistic catalytic mechanism of fast electron transfer of ferrocene and Lewis acid catalysis of metal ions, the AP pyrolysis reaction energy barrier can be efficiently reduced, promoting the redox reaction of NH3 and HClO4, thereby significantly improving the catalytic performance. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 Synthesis route and structure schematic diagram of the trinuclear ferrocene-based metal composite material of the application; Figure 2 a is the DSC curve of pure AP and AP respectively added with 3wt% trinuclear ferrocene-based metal composite material of the application; Figure 2 b is the ln(β / Tp 2 ) -1 linear fitting curve graph of the application; Figure 3 TG-IR combined analysis of AP decomposition products of the application. DETAILED DESCRIPTION

[0032] To enable persons skilled in the art to understand the features and effects of the present application, the following only generally describes and defines the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used herein are understood to have the usual meaning to those skilled in the art of the present application, and in case of conflict, the definition in the specification shall prevail.

[0033] Theories or mechanisms described and disclosed herein, whether correct or not, should not be considered limiting on the scope of the present application, that is, the present application can be practiced without regard to any particular theory or mechanism.

[0034] Herein, all features defined in the form of numerical ranges or percentage ranges such as numerical values, amounts, contents and concentrations are only for the sake of brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions).

[0035] Herein, unless otherwise specified, "comprise", "include", "contain", "have" or similar words encompass the meaning of "consist of" and "consist essentially of", for example, "A comprises a" encompasses the meaning of "A comprises a and other" and "A comprises only a".

[0036] Herein, for the sake of brevity, all possible combinations of the technical features in various embodiments or examples are not described. Therefore, as long as the combinations of the technical features do not contradict each other, the technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered as the scope of the present specification.

[0037] It should be noted that in the present application, the preparation reaction of the burning rate catalyst is completed by means of a homogeneous reactor. The ammonium perchlorate involved is prepared by the laboratory itself. In addition, the drying operation in the whole process is realized by using a vacuum air drying oven.

[0038] The present application will be further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and not to limit the scope of the present application. In addition, it should be understood that after reading the content taught by the present application, those skilled in the art can make various modifications or changes to the present application, and these equivalent forms also fall within the scope defined by the claims attached hereto.

[0039] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" represents weight percentage, "parts" represents parts by weight, and "ratio" represents weight proportion.

[0040] The trinuclear ferrocene-based metal composite material of this invention can precisely cleave NH and Cl-O bonds, enhancing the decomposition of ammonium perchlorate. In its preparation, ferrocene acetaldehyde and ferrocene-based dihydrazones are used as raw materials to first synthesize a novel trinuclear ferrocene ligand, and then a highly active Co is selected. 2+ and Fe 2+ As metal nodes, they complex with ligands to obtain three composite materials: Fc3N4 / CoFe, Fc3N4 / Co, and Fc3N4 / Fe. Their pyrolysis catalytic performance for ammonium perchlorate (AP) was tested by DSC. Compared with existing technologies, this invention has significant advantages: abundant raw material sources, simple preparation, convenient use, and stable performance. Catalytic experiments show that all prepared trinuclear ferrocene-based metal composite materials exhibit superior pyrolysis catalytic performance for AP compared to the traditional ferrocene-based catalyst catorosine.

[0041] Example 1 like Figure 1 As shown, the preparation of Fc3N4 ligand: 1 mmol of ferrocene acetaldehyde (C3N4) was added to a 250 mL three-necked flask. 11 H 10 FeO), 0.5 mmol ferrocene dihydrazone (C 14 H 18 FeN4) and 10 mL of ethanol; heat in an oil bath to 75 °C, reflux with magnetic stirring for 6 h, monitor with TCL, the developing solvent is petroleum ether and ethyl acetate, the volume ratio of petroleum ether and ethyl acetate is 3:1; remove the solvent by rotary evaporation under reduced pressure at 100 °C and a vacuum degree of 1 x 10 Pa, recrystallize using ethanol and water with a volume ratio of 1:1 as solvent, let stand at 4 °C for 12 h, filter to obtain 0.35 g of dark red crystals, yield 78.6%.

[0042] Preparation of Fc3N4 / Co tri-nuclear ferrocene metal composite: 3.0 mmol of Co (NO3)2•6H2O and 2.0 mmol of Fc3N4 were added to 80 mL of DMSO solution to prepare a mixed solution A with a concentration of 0.1 mol / L, and then the mixed solution A was placed in a 200 mL high-pressure reaction kettle, sealed, heated to 120°C and kept for 12 h. After the reaction was completed, the product was cooled to room temperature and centrifuged at a speed of 3000 rpm for 10 min. Then, it was washed with distilled water and ethanol alternately for 3 times, and dried at 60°C to obtain a brown solid powder Fc3N4 / Co.

[0043] Preparation of Fc3N4 / Fe tri-nuclear ferrocene metal composite: 3.0 mmol of Fe (NO3)2•3H2O and 2.0 mmol of Fc3N4 were added to 80 mL of DMSO solution to prepare a mixed solution A with a concentration of 0.1 mol / L, and then the mixed solution A was placed in a 200 mL high-pressure reaction kettle, sealed, heated to 120°C and kept for 12 h. After the reaction was completed, the product was cooled to room temperature and centrifuged at a speed of 3000 rpm for 10 min. Then, it was washed with distilled water and ethanol alternately for 3 times, and dried at 60°C to obtain a black solid powder Fc3N4 / Fe.

[0044] Preparation of Fc3N4 / CoFe tri-nuclear ferrocene metal composite: 1 mmol of Fc3N4 was dissolved in 30 mL of DMSO to prepare a mixed solution A with a concentration of 0.1 mol / L, and then the mixed solution A, 0.5 mmol of Co (NO3)2•6H2O and 0.5 mmol of Fe (NO3)3•3H2O were ultrasonically dissolved for 30 min, transferred to a 100 mL polytetrafluoroethylene high-pressure kettle, and reacted at 140°C for 48 h. After natural cooling, it was filtered, washed with ethanol and distilled water alternately for 3 times, and dried at 80°C under vacuum for 12 h to obtain a dark brown solid powder 0.42 g with a yield of 65.4%. It was detected that the specific surface area of Fc3N4 / Co was 310.60 m 2 / g, the specific surface area of Fc3N4 / Fe was 240.28 m 2 / g, and the specific surface area of Fc3N4 / CoFe was 380.07 m 2 / g.

[0045] As shown in Figure 2 a, the pure AP curve shows two exothermic peaks at 308°C and 442°C, the AP / Fc3N4 curve shows a single exothermic peak at 336°C, the Fc3N4 / Fe curve shows a single exothermic peak at 329°C, the Fc3N4 / Co curve shows a single exothermic peak at 316°C, and the Fc3N4 / CoFe curve shows a single exothermic peak at 290°C.

[0046] As Figure 2 shown in Fig. b, the horizontal axis is 1 / Tp (reciprocal thermodynamic temperature), and the vertical axis is ln(β / Tp 2 ); the fitting slope shows that the activation energy of Fc3N4 / CoFe is the lowest, 67.11 kJ•mol -1 .

[0047] As Figure 3 shown in Fig. a, the decomposition products of pure AP and the corresponding temperatures are as follows: The decomposition of AP (NH4ClO4) is generally divided into two stages, and the following gas products and peak temperatures are detected by TG-IR: 1) 245℃: release of NH3 (ammonia), corresponding to the low-temperature decomposition stage of AP (NH4ClO4→NH3+HClO4); 2) 306℃: release of N2O (nitrous oxide), corresponding to the decomposition of HClO4 (HClO4→N2O+O2+other products); 3) 442℃: release of NO / NO2 (nitrogen oxides), which is the high-temperature decomposition stage of AP.

[0048] The above data show that the decomposition temperature of pure AP is high and the stages are obvious.

[0049] The decomposition product temperature of the composite material of AP and the trinuclear ferrocene metal composite material Fc3N4 / CoFe is shown in Fig. Figure 3 b: When AP is compounded with the trinuclear ferrocene metal composite material Fc3N4 / CoFe, the decomposition peak temperature is significantly advanced, indicating that the catalyst reduces the decomposition activation energy of AP and promotes the reaction: 1) NH3 peak temperature is advanced to 220℃ (originally 245℃), and the catalyst accelerates the proton transfer of NH4 + , promoting the release of NH3; 2) N2O peak temperature is advanced to 280℃ (originally 306℃), and the catalyst promotes the decomposition of HClO4, accelerating the generation rate of N2O; 3) NO / NO2 peak temperature is advanced to 350℃ (originally 442℃), and the catalyst accelerates the generation of nitrogen oxides through redox.

[0050] The above data show that Fc3N4 / CoFe significantly reduces the decomposition temperature of AP, indicating that it improves the thermal decomposition efficiency of AP as a catalyst.

[0051] AP pyrolysis catalytic performance test: Take 0.97 g of AP and 0.03 g of Fc3N4 / CoFe in a agate mortar, add 2 mL of ethanol, grind for 15 min to fine powder; after drying in a vacuum oven at 60℃ for 4h, take 5mg sample in a DSC aluminum crucible, fill the flow rate of 50 mL / min N2 atmosphere, temperature rise at a rate of 10℃ / min from 50-500℃.

[0052] The test results of each compound and the comparison are as follows: The low temperature decomposition temperature (TLTD) of pure AP is 308℃, the high temperature decomposition temperature (THTD) is 442℃, the decomposition heat (ΔH) is 580 J / g, and the apparent activation energy (Ea) is 153.89 kJ•mol -1 ; AP / Fc3N4 has no TLTD data, THTD is 336℃, ΔH is 975 J / g, and Ea is 106.52 kJ•mol -1 ; AP / Fc3N4 / Fe has no TLTD data, THTD is 329℃, ΔH is 1020 J / g, and Ea is 88.68 kJ•mol -1 ; AP / Fc3N4 / Co has no TLTD data, THTD is 316℃, ΔH is 1298 J / g, and Ea is 79.90 kJ•mol -1 ; AP / Fc3N4 / CoFe has no TLTD data, THTD is 290℃, ΔH is 2479 J / g, and Ea is 67.11 kJ•mol -1 .

[0053] In comparison, compared with pure AP, the composite system added with three-nuclear ferrocene-based components has obvious changes in thermal decomposition performance. In terms of THTD, the composite system is lower than pure AP, and the THTD of AP / Fc3N4 / CoFe is the lowest, indicating that its high temperature decomposition starts earliest; in terms of ΔH, the composite system is higher than pure AP, among which the ΔH of AP / Fc3N4 / CoFe is the largest, indicating that it releases the most energy in the decomposition process; in terms of Ea, the composite system is lower than pure AP, and the Ea of AP / Fc3N4 / CoFe is the smallest, meaning that its decomposition reaction is easier to occur. Overall, AP / Fc3N4 / CoFe performs best in promoting the thermal decomposition of AP. As shown in Table 1: Table 1: Test results of three-nuclear ferrocene metal composite on catalytic decomposition performance of AP

[0054] Comparative Example 1 Comparison of traditional ferrocene derivatives migration: Sample: Katoxin (2,2-bis(ethylferrocene)propane), Fc3N4 / CoFe.

[0055] Preparation method: 10 mg of sample was placed on filter paper, and stored in an oven at 60 ℃ for 30 days. The diffusion radius was measured.

[0056] Test results: The diffusion radius of Katoxin was 5.2 mm, and no migration of Fc3N4 / CoFe was detected.

[0057] Example 2 Preparation of Fc3N4 ligand: 1.5 mmol of ferrocene acetaldehyde (C 11 H 10 FeO), 0.7 mmol of ferrocenyl bis-hydrazone (C 14 H 18 FeN4), and 10 mL of ethanol were added to a 250 mL three-necked flask. The oil bath was heated to 70 ℃, and the mixture was stirred magnetically under reflux for 7 h. TLC monitoring was performed using petroleum ether and ethyl acetate as the developing agent (volume ratio of 3:1). The solvent was evaporated under reduced pressure using a rotary evaporator at a temperature of 110 ℃ and a vacuum degree of 1x10 Pa. The product was recrystallized using ethanol and water (volume ratio of 1:1) as the solvent, and was allowed to stand at 4 ℃ for 12 h. The dark red crystals were obtained by suction filtration, and the yield was 0.35 g, i.e., 78.6%. Preparation of Fc3N4 / Co ferrocenyl metal composite: 1.0 mmol of Co(NO3)2•6H2O and 1.0 mmol of Fc3N4 were added to 80 mL of DMSO to prepare a mixed solution A with a concentration of 0.15 mol / L. Then, the mixed solution A was placed in a 200 mL high-pressure reaction kettle, which was sealed and heated to 120 ℃ for 12 h. After the reaction was completed, the product was cooled to room temperature and centrifuged at a speed of 2000 rpm for 5 min. Then, the product was washed with distilled water and ethanol alternately for 3 times, and was dried at 60 ℃ to obtain a brown solid powder Fc3N4 / Co.

[0058] Preparation of Fc3N4 / Fe ferrocenyl metal composite: 3.0 mmol of Fe(NO3)2•3H2O and 2.0 mmol of Fc3N4 were added to 80 mL of DMSO to prepare a mixed solution A with a concentration of 0.15 mol / L. Then, the mixed solution A was placed in a 200 mL high-pressure reaction kettle, which was sealed and heated to 120 ℃ for 12 h. After the reaction was completed, the product was cooled to room temperature and centrifuged at a speed of 2000 rpm for 5 min. Then, the product was washed with distilled water and ethanol alternately for 3 times, and was dried at 60 ℃ to obtain a black solid powder Fc3N4 / Fe.

[0059] Preparation of Fc3N4 / CoFe ferrocenyl metal composite: A mixture solution A with a concentration of 0.15 mol / L was prepared by dissolving 1 mmol Fc3N4 in 30 mL DMSO. The mixture solution A, 0.5 mmol Co(NO3)2·6H2O and 0.5 mmol Fe(NO3)2·3H2O were ultrasonically dissolved for 30 min, and then transferred into a 100 mL polytetrafluoroethylene autoclave. The autoclave was kept at 140 °C for 48 h. After natural cooling, the product was centrifuged at 2000 rpm for 5 min, washed with ethanol and distilled water for 3 times, and dried at 80 °C under vacuum for 12 h. A dark brown powder with a yield of 65.4% was obtained.

[0060] Example 3 Preparation of Fc3N4 ligand: A 250 mL three-necked flask was charged with 2 mmol ferrocenyl acetaldehyde (C 11 H 10 FeO), 1 mmol ferrocenyl bis-hydrazone (C 14 H 18 FeN4) and 10 mL ethanol. The flask was heated to 80 °C in an oil bath with magnetic stirring for 8 h. The reaction was monitored by TLC with petroleum ether and ethyl acetate (3:1, by volume) as the developing solvent. The solvent was removed by rotary evaporation at 120 °C and 1x10 2 Pa. The product was recrystallized from a 1:1 (by volume) mixture of ethanol and water at 4 °C for 12 h. A dark red crystal with a yield of 78.6% was obtained after filtration.

[0061] Preparation of Fc3N4 / Co trinuclear ferrocenyl metal composite: 3.0 mmol Co(NO3)2·6H2O and 2.0 mmol Fc3N4 were added to 80 mL DMSO to prepare a mixture solution A with a concentration of 0.2 mol / L. The mixture solution A was then placed in a 200 mL high-pressure reactor, which was sealed and heated to 120 °C for 12 h. After the reaction was completed, the product was cooled to room temperature and centrifuged at 4000 rpm for 15 min. The product was then washed with ethanol and ethanol for 3 times, and dried at 60 °C to obtain a brown solid powder Fc3N4 / Co.

[0062] Preparation of Fc3N4 / Fe trinuclear ferrocenyl metal composite: 3.0 mmol Fe(NO3)2·3H2O and 2.0 mmol Fc3N4 were added to 80 mL DMSO to prepare a mixture solution A with a concentration of 0.2 mol / L. The mixture solution A was then placed in a 200 mL high-pressure reactor, which was sealed and heated to 120 °C for 12 h. After the reaction was completed, the product was cooled to room temperature and centrifuged at 4000 rpm for 15 min. The product was then washed with distilled water and ethanol for 3 times, and dried at 60 °C to obtain a black solid powder Fc3N4 / Fe.

[0063] Preparation of Fc3N4 / CoFe tri-core ferrocene-based metal composite: 1mmol Fc3N4 was dissolved in 30mL DMSO to prepare a mixed solution A with a concentration of 0.2mol / L, the mixed solution A, 0.5mmol Co(NO3)2·6H2O and 0.5mmol Fe(NO3)2·3H2O were ultrasonically dissolved for 30min, and then transferred to a 100mL polytetrafluoroethylene autoclave for constant temperature reaction at 140℃ for 48h; after natural cooling, the product was extracted by filtration, centrifuged at a speed of 4000rpm for 15min, washed with ethanol and distilled water alternately for 3 times, and dried at 80℃ under vacuum for 12h to obtain 0.42g of dark brown solid powder with a yield of 65.4%. The above is only to illustrate the technical idea of the present application, and cannot limit the protection scope of the present application. Any modification made according to the technical idea of the present application on the basis of the technical scheme falls within the protection scope of the claims of the present application.

Claims

1. A method for preparing a trinuclear ferrocene-based metal composite material, characterized in that, Includes the following steps: 1) After dissolving ferrocene acetaldehyde and ferrocene-based bishydrazone, the mixture was heated under reflux and purified to obtain the trinuclear ferrocene ligand Fc3N4; 2) Dissolve the trinuclear ferrocene ligand Fc3N4 in a solvent to prepare a mixed solution A with a concentration of (0.1-0.2) mol / L; 3) Divide the mixture A into three equal parts and add Co salt solution, Fe salt solution and mixed solution of Co salt and Fe salt respectively to obtain trinuclear ferrocene-based metal composite materials of Fc3N4 / Co, Fc3N4 / Fe and Fc3N4 / CoFe respectively.

2. The method for preparing a trinuclear ferrocene-based metal composite material according to claim 1, characterized in that, In step 1), the molar ratio of ferrocene acetaldehyde and ferrocene-based dihydrazone is (1-2):(0.5-1); in step 3), the molar ratio of Co salt and Fe salt in the mixed solution is 1:1; the relationship between the amount of mixed solution A and the mixed solution of Co salt and Fe salt is: 1 mmol of trinuclear ferrocene ligand Fc3N4 corresponds to 1 mmol of Co salt and 1 mmol of Fe salt; the relationship between the amount of mixed solution A and Co salt solution is: 1 mmol of trinuclear ferrocene ligand Fc3N4 corresponds to 1 mmol of Co salt; the relationship between the amount of mixed solution A and Fe salt solution is: 1 mmol of trinuclear ferrocene ligand Fc3N4 corresponds to 1 mmol of Fe salt.

3. The method for preparing a trinuclear ferrocene-based metal composite material according to claim 1, characterized in that, In step 3), the Co salt in the Co salt solution is Co(NO3)2•6H2O, and the Fe salt in the Fe salt solution is Fe(NO3)2•3H2O; the Co salt in the mixed solution of Co salt and Fe salt is Co(NO3)2•6H2O, and the Fe salt is Fe(NO3)2•3H2O.

4. The method for preparing a trinuclear ferrocene-based metal composite material according to claim 1, characterized in that, In step 1), the heating temperature is 70-80℃ and the reaction time is 5-8h.

5. The method for preparing a trinuclear ferrocene-based metal composite material according to claim 1, characterized in that, The purification process includes a vacuum distillation solvent removal process and a recrystallization process. In the vacuum distillation solvent removal process, step 1) involves a temperature of 100-120°C and a vacuum degree of 1x10⁻¹⁰ to 1x10⁻¹⁰. 2 Pa; In the recrystallization process, ethanol and water are used as a mixed solvent, with a volume ratio of ethanol to water of 1:

1.

6. The method for preparing a trinuclear ferrocene-based metal composite material according to claim 1, characterized in that, In step 2), the mixture A is heated, cooled, centrifuged, washed and dried.

7. The method for preparing a trinuclear ferrocene-based metal composite material according to claim 6, characterized in that, The heating temperature is 110-130℃, and the reaction time is 11-13h.

8. The method for preparing a trinuclear ferrocene-based metal composite material according to claim 6, characterized in that, Centrifugation conditions: 2000-4000 rpm, 5-15 min.

9. The trinuclear ferrocene-based metal composite material prepared by the preparation method of any one of claims 1 to 8.

10. The application of the trinuclear ferrocene-based metal composite material according to claim 9 in the pyrolysis of ammonium perchlorate.

Images