Method for catalytically synthesizing dicyclopropane high-energy fuel by Pd fullerene

Abstract

The invention provides a method for catalytic synthesis of a dicyclopropane high-energy fuel from Pd fullerene, belongs to the technical field of high-energy fuel synthesis, and aims to solve the technical problems of low conversion rate and low dicycloproduct selectivity in preparation of the dicyclopropane high-energy fuel from norbornadiene. The preparation method comprises the following steps: mixing a Pd / fullerene catalyst, norbornadiene, an organic solvent and alkali liquor, adding a diazo precursor for reaction, and then extracting, separating and drying a reaction solution to finally obtain a bicyclic product. The Pd electronic state is regulated and controlled by utilizing the strong electron withdrawing effect of fullerene, so that the dicyclic product selectivity of norbornadiene is improved, and the method has high conversion rate (gt; 99%) and a high bicyclic product selectivity (gt; 86%). The method is mild in reaction and simple in process, can quickly obtain the dicyclopropane-based high-energy fuel, and has the advantages that the catalyst can be recycled and the like compared with a homogeneous catalysis system. The high-efficiency and accurate synthesis of the dicyclopropane high-energy fuel is beneficial to the continuous progress of China in the field of aeronautics and astronautics.

Description

Technical Field

[0001] The present invention belongs to the technical field of high-energy fuel synthesis, and particularly relates to a bicyclopropyl high-energy fuel. Background Art

[0002] As the fundamental energy source of the propulsion system, high-energy aerospace fuels directly affect the payload capacity and mission range of aircraft. Compared with common ordinary hydrocarbon fuels, the molecules of cyclopropyl high-energy fuels have angle strain and torsional strain energy, making them have higher density and volumetric calorific value, providing higher energy within a limited oil-phase volume, and having broad development and application prospects.

[0003] Patent Publication No. CN 118388307 A discloses a method for highly selectively synthesizing bicyclopropyl high-energy fuel. A Pd / graphene single-site catalyst, dicyclopentadiene, an organic solvent, and an alkali solution are mixed, and a diazo precursor is added to react in an inert gas atmosphere. After the reaction, a two-phase solution is obtained, and the bicyclic product is prepared by extraction and separation. This patent improves the yield of the bicyclic product to a certain extent. However, dicyclopentadiene usually comes from the C5 fraction of kerosene or petroleum cracking, and its supply is affected by the petrochemical industry, and the supply may be unstable. Moreover, the production process of dicyclopentadiene is relatively complex and requires processing and purification through multiple processes, resulting in a relatively high production cost.

[0004] In addition to using dicyclopentadiene to synthesize dicyclopropyl high-energy fuel, there are also some reports on using norbornadiene as a raw material. However, the method of synthesizing the corresponding dicyclopropyl high-energy fuel from norbornadiene currently mainly has the problems of low raw material conversion rate and low selectivity of dicyclic products. For example, the journal paper Journal of the American Chemical Society, 1964, 86, 1347-1356 first used the same molar equivalent of Zn-Cu couple catalyst to catalyze the cyclopropanation reaction of norbornadiene, and the results showed that almost no dicyclic product was formed; the journal paper Bulletin of the Academy of Sciences of the USSR, 1989, 38, 1707-1714 reported that Pd(acac)2 was used as a catalyst to catalyze the cyclopropanation of norbornadiene in diethyl ether solvent at -10 °C. The reaction results showed that the conversion rate of norbornadiene was 40%, the selectivity of monocyclic product was 32%, and the selectivity of dicyclic product was 24%; the journal paper Bulletin of the Korean Chemical Society, 2007, 28, 322-324 disclosed that Zn powder was used to catalyze the reaction of norbornadiene with CH2I2 to form the corresponding dicyclic product, and its yield was only 10%; the journal paper Chemical Engineering Science, 2024, 283, 119366 used the solid acid catalyst HPW / MCM-41 and CH2I2 as the carbene precursor to catalyze the cyclopropanation reaction of norbornadiene. The reaction conversion rate was 98%, and the selectivity of dicyclic product was 33.4%. The journal paper Industrial & Engineering Chemistry Research, 2021, 60, 10978-10987 reported the cyclopropanation reaction of norbornadiene with CH2I2 catalyzed by Et2Zn. The selectivity of dicyclic product in this reaction could reach 84.9%, but the amount of Et2Zn used was large (4 times the molar amount of norbornadiene), the conditions were harsh and dangerous, and it could not be recycled. Summary of the Invention

[0005] Aiming at the technical problems of low raw material conversion rate and low selectivity of dicyclic products in the dicyclopropyl high-energy fuel prepared from norbornadiene at present, the present invention provides a method for synthesizing dicyclopropyl high-energy fuel catalyzed by Pd fullerene (C 60 / Pd x ), which has the advantages of high raw material conversion rate, high selectivity of dicyclic products, simple reaction process, mild conditions, recyclability, etc.

[0006] In order to achieve the above object, the technical solution of the present invention is realized as follows:

[0007] A method for catalytic synthesis of bicyclopropyl high-energy fuel using Pd fullerene, comprising the following steps: mixing Pd / fullerene catalyst, norbornadiene, organic solvent and alkali solution, adding a diazo precursor for reaction, and subjecting the reaction solution to extraction separation and drying to obtain a bicyclic product.

[0008] The preparation method of the Pd / fullerene catalyst is as follows: dropping a palladium source solution into a fullerene solution, and Pd is loaded on the fullerene in the form of nanoclusters, and the Pd / fullerene catalyst is obtained through filtration and drying.

[0009] The palladium source is any one of palladium diacetylacetonate, palladium acetate, tris(dibenzylideneacetone)dipalladium-chloroform adduct.

[0010] The molar ratio of Pd to fullerene in the Pd / fullerene catalyst is 0.1 - 10.

[0011] The diazo precursor is one or more of N-methyl-N-nitrosourea, N-methyl-N-nitroso-p-toluenesulfonamide or N-methyl-N-nitroso-N'-nitroguanidine.

[0012] The organic solvent is one or more of n-hexane, cyclohexane, dichloromethane.

[0013] The alkali solution is an aqueous solution of potassium hydroxide or sodium hydroxide, with a concentration of 15wt% - 60wt%.

[0014] The molar ratio of norbornadiene to the diazo precursor is 1:2 - 1:8, the amount of substance of Pd in the Pd / fullerene catalyst is 0.2 - 1.2mol% of norbornadiene, and the amount of substance of hydroxide in the alkali solution is 5 - 20 times that of norbornadiene.

[0015] The concentration of norbornadiene in the organic solvent is 0.2 - 0.5mol / L.

[0016] The temperature of the reaction is -20 - 60°C, and the time is 0.5 - 4h.

[0017] The beneficial effects of the present invention: The present invention uses Pd / fullerene (C 60 / Pd x ) catalyst to significantly improve the raw material conversion rate and the selectivity of the bicyclic product. The conversion rates can all reach more than 79%, and the highest can reach more than 99%; the selectivities can all reach more than 65%, and the highest can reach more than 90%. This significant improvement is due to the strong electron-withdrawing effect of fullerene, which regulates the electronic state of Pd atoms, thereby improving the raw material conversion rate and the selectivity of the bicyclic product. In addition, compared with the prior art, the present invention also has the advantages of simple reaction process, mild conditions, recyclability, etc. The efficient synthesis of bicyclopropyl high-energy fuel will contribute to faster progress of our country in the aerospace field. Brief Description of the Drawings

[0018] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0019] Figure 1 It is the reaction equation of norbornadiene cyclopropanation.

[0020] Figure 2 It is the comparison of the catalytic performance of Pd / fullerene catalyst with the condition of no catalyst and commercial Pd / C catalyst under the same reaction conditions.

[0021] Figure 3 It is the differential charge calculation diagram of Pd / fullerene catalyst. Detailed Embodiments

[0022] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0023] The preparation method of the Pd / fullerene (C 60 / Pd4) catalyst used in the following Examples 1-12 is as follows: Dissolve 649 mg of C 60 completely in 400 mL of toluene, and then dissolve 1.863 g of Pd2(dba)3CHCl3 in 400 mL of toluene to form a clear solution. Under vigorous stirring, slowly drop the toluene solution of Pd2(dba)3CHCl3 into the toluene solution of C 60 . Under N2, stir the mixture at room temperature for 24 h, obtain a black precipitate, and collect it by filtration to obtain C 60 / Pd4.

[0024] The preparation method of the Pd / fullerene (C 60 / Pd3) catalyst used in the following Example 13 is as follows: Dissolve 649 mg of C 60 completely in 400 mL of toluene, and then dissolve 1.397 g of Pd2(dba)3CHCl3 in 400 mL of toluene to form a clear solution. Under vigorous stirring, slowly drop the toluene solution of Pd2(dba)3CHCl3 into C 60in a toluene solution. Under N2, the mixture was stirred at room temperature for 24 h, and then a black precipitate was obtained and collected by filtration to obtain C 60 / Pd3.

[0025] The commercial palladium on activated carbon (Pd / C) catalyst used in Comparative Example 2 below was purchased from Shanghai Macklin Biochemical Co., Ltd., and the Pd mass content was 10 wt%.

[0026] Example 1

[0027] A method for catalytic synthesis of bicyclopropyl high-energy fuel by Pd fullerene, and the norbornadiene cyclopropanation reaction equation is as Figure 1 shown (X in the figure represents different palladium contents, and X is 4 in this example), including the following steps: At room temperature, first add 18 mL of CH2Cl2 solvent to a flask, then add 0.61 mL of norbornadiene, 1 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 2.47 g of N-methyl-N-nitrosourea. After reacting at room temperature of 20 °C for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction.

[0028] Let it stand for layering to obtain a two-phase solution, then extract and separate, and finally use gas chromatography to measure the concentrations of each component in the organic phase, and calculate that the conversion rate is 99.6% and the selectivity of the bicyclic product is 86.0%.

[0029] Example 2

[0030] A method for catalytic synthesis of bicyclopropyl high-energy fuel by Pd fullerene, including the following steps: At room temperature, first add 18 mL of CH2Cl2 solvent to a flask, then add 0.61 mL of norbornadiene, 0.4 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 2.47 g of N-methyl-N-nitrosourea. After reacting at room temperature of 20 °C for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand for layering to obtain a two-phase solution, then extract and separate.

[0031] Example 3

[0032] A method for catalytic synthesis of bicyclopropyl high-energy fuel by Pd fullerene, including the following steps: At room temperature, first add 18 mL of CH2Cl2 solvent to a flask, then add 0.61 mL of norbornadiene, 0.6 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 2.47 g of N-methyl-N-nitrosourea. After reacting at room temperature of 20 °C for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand for layering to obtain a two-phase solution, then extract and separate.

[0033] Example 4

[0034] A method for catalytic synthesis of dicyclopropyl high-energy fuel by Pd fullerene, comprising the following steps: At room temperature, first add 18 mL of CH2Cl2 solvent into a flask, then add 0.61 mL of norbornadiene, 0.8 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 2.47 g of N-methyl-N-nitrosourea. After reacting at room temperature of 20 °C for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand and separate into two-phase solution, and then extract and separate.

[0035] Example 5

[0036] A method for catalytic synthesis of dicyclopropyl high-energy fuel by Pd fullerene, comprising the following steps: At room temperature, first add 18 mL of CH2Cl2 solvent into a flask, then add 0.61 mL of norbornadiene, 1.2 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 2.47 g of N-methyl-N-nitrosourea. After reacting at room temperature of 20 °C for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand and separate into two-phase solution, and then extract and separate.

[0037] Example 6

[0038] A method for catalytic synthesis of dicyclopropyl high-energy fuel by Pd fullerene, comprising the following steps: At 0 °C, first add 18 mL of CH2Cl2 solvent into a flask, then add 0.61 mL of norbornadiene, 1.0 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 2.47 g of N-methyl-N-nitrosourea. After reacting for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand and separate into two-phase solution, and then extract and separate.

[0039] Example 7

[0040] A method for catalytic synthesis of dicyclopropyl high-energy fuel by Pd fullerene, comprising the following steps: At 10 °C, first add 18 mL of CH2Cl2 solvent into a flask, then add 0.61 mL of norbornadiene, 1.0 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 2.47 g of N-methyl-N-nitrosourea. After reacting for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand and separate into two-phase solution, and then extract and separate.

[0041] Example 8

[0042] A method for catalytic synthesis of dicyclopropyl high-energy fuel by Pd fullerene, comprising the following steps: At 30 °C, first add 18 mL of CH2Cl2 solvent to a flask, then add 0.61 mL of norbornadiene, 1.0 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 2.47 g of N-methyl-N-nitrosourea. After reacting for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand for layering to obtain a two-phase solution, and then perform extraction and separation.

[0043] Example 9

[0044] A method for catalytic synthesis of dicyclopropyl high-energy fuel by Pd fullerene, comprising the following steps: At room temperature, first add 18 mL of CH2Cl2 solvent to a flask, then add 0.61 mL of norbornadiene, 1.0 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 1.24 g of N-methyl-N-nitrosourea. React at room temperature of 20 °C for 2 h, then add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand for layering to obtain a two-phase solution, and then perform extraction and separation.

[0045] Example 10

[0046] A method for catalytic synthesis of dicyclopropyl high-energy fuel by Pd fullerene, comprising the following steps: At room temperature, first add 18 mL of CH2Cl2 solvent to a flask, then add 0.61 mL of norbornadiene, 1.0 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 1.85 g of N-methyl-N-nitrosourea. React at room temperature of 20 °C for 2 h, then add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand for layering to obtain a two-phase solution, and then perform extraction and separation.

[0047] Example 11

[0048] A method for catalytic synthesis of dicyclopropyl high-energy fuel by Pd fullerene, comprising the following steps: At room temperature, first add 18 mL of CH2Cl2 solvent to a flask, then add 0.61 mL of norbornadiene, 1.0 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 3.09 g of N-methyl-N-nitrosourea. React at room temperature of 20 °C for 2 h, then add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand for layering to obtain a two-phase solution, and then perform extraction and separation.

[0049] Example 12

[0050] A method for catalytic synthesis of bicyclopropyl high-energy fuel by Pd fullerene, comprising the following steps: At room temperature, first add 18 mL of CH2Cl2 solvent into a flask, then add 0.61 mL of norbornadiene, 1.0 mol% C 60 / Pd4 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 3.71 g of N-methyl-N-nitrosourea. After reacting at 20 °C for 2 h at room temperature, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand for layering to obtain a two-phase solution, and then perform extraction and separation.

[0051] The conversion rates and selectivities of bicyclic products in Examples 2-12 are shown in Table 1.

[0052] Table 1 Examples 2-12

[0053]

[0054]

[0055] Example 13

[0056] A method for catalytic synthesis of bicyclopropyl high-energy fuel by Pd fullerene, comprising the following steps: At room temperature, first add 18 mL of CH2Cl2 solvent into a flask, then add 0.61 mL of norbornadiene, 1.0 mol% C 60 / Pd3 catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 2.47 g of N-methyl-N-nitrosourea. After reacting at 20 °C for 2 h at room temperature, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand for layering to obtain a two-phase solution, and then perform extraction and separation. The calculated conversion rate is 96.4%, the selectivity of monocyclic product is 16.1%, and the selectivity of bicyclic product is 75.9%.

[0057] Comparative Example 1

[0058] To compare the catalytic effects of Pd / fullerene catalysts, a comparative experiment was carried out under catalyst-free conditions.

[0059] At room temperature, first add 18 mL of CH2Cl2 solvent into a flask, then add 0.61 mL of norbornadiene, 9.8 g of 50 wt% KOH solution, and then slowly add 2.47 g of N-methyl-N-nitrosourea. After reacting for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand for layering to obtain a two-phase solution, and then perform extraction and separation. Finally, use gas chromatography to determine the concentrations of each component in the organic phase, and the calculated conversion rate is 11.4%, the selectivity of monocyclic product is 0.8%, and the selectivity of bicyclic product is 0.3%.

[0060] Comparative Example 2

[0061] To compare the catalytic performance of the Pd / fullerene catalyst, a comparative experiment was carried out under commercial 10 wt% Pd / C.

[0062] At room temperature, first add 18 mL of CH2Cl2 solvent to a flask, then add 0.61 mL of norbornadiene, 123.7 mg of 10 wt% Pd / C catalyst, 9.8 g of 50 wt% KOH solution, and then slowly add 2.47 g of N-methyl-N-nitrosourea. After reacting for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction.

[0063] Let it stand for layering to obtain a two-phase solution, then extract and separate. Finally, use gas chromatography to measure the concentrations of each component in the organic phase. The calculated conversion rate is 29.6%, the selectivity of the monocyclic product is 71.6%, and the selectivity of the bicyclic product is 27.3%.

[0064] The catalytic performances of Example 1, Example 13 and the comparative example are as shown in the appendix Figure 2 As shown, under the condition of no catalyst, the conversion rate of norbornadiene is only 11.4%, and almost no bicyclic product is formed; under the commercial Pd / C catalyst, the conversion rate is increased to 29.6%, and the selectivity of the bicyclic product is 27.3%; under the C 60 / Pd3 catalyst, the conversion rate is increased to 96.4%, and the selectivity of the bicyclic product is 75.9%; while under the C 60 / Pd4 catalyst, the conversion rate is 99.6%, and the selectivity of the bicyclic product is further increased to 86.0%, indicating that the electron-withdrawing effect of fullerene in the Pd / fullerene catalyst can significantly regulate the electronic state of Pd, thereby improving the selectivity of the bicyclic product.

[0065] According to the first-principles and density functional (DFT) theory, using the VASP5.4.4 software, the molecular structure of Pd / fullerene was optimized under the Perdew-Burke-Ernzerhof functional (GGA-PBE) (as shown in the appendix Figure 3 ). Figure 3 The differential charge of Pd / fullerene was calculated, where the blue and yellow regions represent the regions of electron reduction and enrichment respectively. The results show that there is a strong electron exchange interaction between fullerene and Pd nanoclusters. According to the Bader charge calculation, 0.32 electrons are transferred from the Pd nanoclusters to the fullerene. The calculation shows that fullerene can form a Pd-C coordination structure with Pd and cause a change in the electronic state of Pd, thereby improving the conversion rate of norbornadiene and the selectivity of the bicyclic product.

[0066] Example 14

[0067] A method for catalytic synthesis of bicyclopropyl high-energy fuel with Pd fullerene, comprising the following steps: adding 649 mg of C 60Fully dissolve it in 400 mL of toluene, and then dissolve 9.315 g of Pd2(dba)3CHCl3 in 400 mL of toluene to form a clear solution. Under vigorous stirring, slowly drip the toluene solution of Pd2(dba)3CHCl3 into the toluene solution of C 60 After stirring the mixture at room temperature for 24 h under N2, a black precipitate is obtained and collected by filtration to obtain C 60 / Pd.

[0068] At room temperature, first add 16 mL of n-hexane to a flask, then add 0.61 mL of norbornadiene, 1.0 mol% of C 60 / Pd catalyst, 10.8 g of 60 wt% KOH solution, and then slowly add 3.53 g of N-methyl-N-nitroso-N′-nitroguanidine. After reacting at room temperature of 20 °C for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand for layering to obtain a two-phase solution, and then extract and separate.

[0069] Example 15

[0070] A method for catalytic synthesis of dicyclopropyl high-energy fuel by Pd fullerene, comprising the following steps: Dissolve 649 mg of C 60 Fully dissolve it in 400 mL of toluene, and then dissolve 0.093 g of Pd2(dba)3CHCl3 in 400 mL of toluene to form a clear solution. Under vigorous stirring, slowly drip the toluene solution of Pd2(dba)3CHCl3 into the toluene solution of C 60 After stirring the mixture at room temperature for 24 h under N2, a black precipitate is obtained and collected by filtration to obtain C 60 / Pd4.

[0071] At room temperature, first add 30 mL of cyclohexane to a flask, then add 0.61 mL of norbornadiene, 1.0 mol% of C 60 / Pd4 catalyst, 7.8 g of 15 wt% NaOH solution, and then slowly add 4.07 g of N-methyl-N-nitroso-p-toluenesulfonamide. After reacting at room temperature of 20 °C for 2 h, add 24 mL of dilute hydrochloric acid to quench the reaction. Let it stand for layering to obtain a two-phase solution, and then extract and separate.

[0072] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for catalytic synthesis of bicyclopropyl high-energy fuel by Pd fullerene, characterized in that, It includes the following steps: Mix the Pd / fullerene catalyst, norbornadiene, organic solvent and alkali solution, add a diazo precursor for reaction, and after extraction, separation and drying of the reaction solution, a bicyclic product is obtained.

2. The method for catalytic synthesis of bicyclopropyl high-energy fuel with Pd fullerene according to claim 1, characterized in that, The preparation method of the Pd / fullerene catalyst is as follows: drop a palladium source solution into a fullerene solution, and obtain the Pd / fullerene catalyst through filtration and drying.

3. The method for catalytic synthesis of bicyclopropyl high-energy fuel with Pd fullerene according to claim 2, characterized in that, The palladium source is any one of palladium diacetylacetonate, palladium acetate, and tris(dibenzylideneacetone)dipalladium-chloroform adduct.

4. The method for catalytic synthesis of bicyclopropyl high-energy fuel using Pd fullerene according to claim 3, characterized in that The molar ratio of Pd to fullerene in the Pd / fullerene catalyst is 0.1 - 10.

5. The method for catalytic synthesis of bicyclopropyl high-energy fuel with Pd fullerene according to any one of claims 1-4, characterized in that, The diazo precursor is one or more of N-methyl-N-nitrosourea, N-methyl-N-nitroso-p-toluenesulfonamide, or N-methyl-N-nitroso-N'-nitroguanidine.

6. The method for catalytic synthesis of bicyclopropyl high-energy fuel using Pd fullerene according to claim 5, characterized in that The organic solvent is one or more of n-hexane, cyclohexane, and dichloromethane.

7. The method for catalytic synthesis of bicyclopropyl high-energy fuel with Pd fullerene according to claim 6, characterized in that The alkali solution is an aqueous solution of potassium hydroxide or sodium hydroxide, with a concentration of 15wt% - 60wt%.

8. The method for catalytic synthesis of bicyclopropyl high-energy fuel by Pd fullerene according to claim 7, wherein The molar ratio of norbornadiene to the diazo precursor is 1:2 - 1:8, the amount of substance of Pd in the Pd / fullerene catalyst is 0.2 - 1.2 mol% of norbornadiene, and the amount of substance of hydroxide ions in the alkali solution is 5 - 20 times that of norbornadiene.

9. The method for catalytic synthesis of bicyclopropyl high-energy fuel by Pd fullerene according to claim 1, characterized in that The concentration of norbornadiene in the organic solvent is 0.2 - 0.5 mol / L.

10. The method for catalytic synthesis of bicyclopropyl high-energy fuel with Pd fullerene according to claim 1, wherein The temperature of the reaction is -20 - 60 °C, and the time is 0.5 - 4 h.

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