Application of catalysts in the synthesis of polymeric COH energetic materials and their synthesis methods

Abstract

The present invention discloses the use of a catalyst in the synthesis of a polymerized COH energetic material and a synthesis method. This invention relates to the field of energetic materials technology and addresses the technical issues of existing polymerized COH material synthesis techniques, which require high pressures, harsh synthesis conditions, and are difficult to implement. The present synthesis method incorporates a catalyst during a high-pressure reaction to reduce the pressure required to synthesize the polymerized COH energetic material. The catalyst comprises a precious metal or a precious metal-loaded copper oxide or ceria material; preferably, the precious metal comprises palladium, platinum, ruthenium, rhodium, or gold. The present synthesis method requires relatively low pressures, making it amenable to industrial production.

Description

Technical Field

[0001] The present invention belongs to the technical field of energetic materials, and in particular relates to the application of a catalyst in the synthesis of polymerized COH energetic materials and a synthesis method. Background Art

[0002] The disruptive energetic materials currently under research include metallic hydrogen, all-nitrogen compounds, and high-tension bond energy release materials. Theoretical predictions show that the energy density of metallic hydrogen is about 2.16×10 5 Joules per gram, making it the explosive with the highest chemical energy known to date. Due to its high energy density, metallic hydrogen can be used as an ultra-high-yield explosive, with an equivalent of 50 times that of the first-generation explosive TNT, possessing significant military and civilian applications. Unfortunately, the current synthesis of metallic hydrogen requires extremely high pressures (above ~400 GPa), and direct evidence of its existence remains unavailable. As high-energy-density energetic materials, all-nitrogen compounds face the challenge of recovering them at ambient pressure. High-tension bond energy release materials are solid polymers formed from gaseous molecular compounds under the action of condensed matter physics. Currently, a limited number of studies have focused on polymerized COH energetic materials. However, current technologies require relatively high pressures to synthesize polymerized COH materials. While these pressures are readily achievable in the laboratory, these conditions limit their mass production. Researchers are actively pursuing methods to synthesize polymerized COH materials at lower pressures for engineering applications. Summary of the Invention

[0003] In view of the above analysis, the present invention aims to provide an application of a catalyst in the synthesis of polymerized COH energetic materials and a synthesis method to solve the following technical problems: the synthesis technology of polymerized COH materials in the existing technology requires high pressure and harsh synthesis conditions, which are difficult to achieve.

[0004] The purpose of the present invention is mainly achieved through the following technical solutions:

[0005] On the one hand, the present invention discloses an application of a catalyst in the synthesis of polymerized COH energetic materials, wherein the catalyst includes a precious metal or a precious metal-loaded copper oxide or cerium dioxide material. The catalyst is used in the synthesis of polymerized COH energetic materials, thereby reducing the pressure required for the synthesis of polymerized COH energetic materials.

[0006] Furthermore, the noble metal includes palladium, platinum, ruthenium, rhodium or gold.

[0007] On the other hand, the present invention also discloses a method for synthesizing a polymerized COH energetic material. The synthesis method comprises adding a catalyst to a high-pressure reaction to reduce the pressure required for synthesizing the polymerized COH energetic material; the catalyst comprises a noble metal or a noble metal-supported copper oxide or a cerium dioxide material;

[0008] Preferably, the noble metal includes palladium, platinum, ruthenium, rhodium or gold.

[0009] Furthermore, the synthesis method comprises the following steps:

[0010] S1. Loading H2 and CO gases into a high-pressure chamber, and then sealing the high-pressure chamber; wherein a catalyst is placed in the high-pressure chamber;

[0011] S2. Pressurize the H2 and CO gases in the high-pressure chamber, maintain the target pressure for a period of time, then unload the pressure, open the high-pressure chamber, and obtain a polymerized COH energetic material.

[0012] Furthermore, S1 includes:

[0013] S11. Complete the preparation work for the pressurized accessories of the high-pressure device;

[0014] S12, assembling the pressurized accessories of the high-pressure device into the thermostat cavity, and sealing the thermostat cavity;

[0015] S13, loading a mixture of carbon monoxide and hydrogen into the high-pressure chamber, and then sealing the high-pressure chamber by adjusting the relative positions of an upper anvil and a lower anvil of the high-pressure device;

[0016] S14. Release the remaining carbon monoxide and hydrogen in the thermostat cavity and remove the pressurizing accessories of the high-pressure device.

[0017] Furthermore, it also includes:

[0018] S3, placing the polymerized COH energetic material obtained in S2 into a high-pressure cavity; wherein a catalyst is placed in the high-pressure cavity;

[0019] S4, liquefying the carbon monoxide gas to fill the high-pressure cavity in S3, and then sealing the high-pressure cavity;

[0020] S5. Pressurize the material in the high-pressure cavity in S4 until the target pressure is reached, maintain the pressure, then unload the pressure and open the high-pressure cavity to obtain the improved polymerized COH energetic material.

[0021] Furthermore, in S1, the catalyst is deposited in the high-pressure cavity in the form of a thin film.

[0022] Furthermore, in S1, the thickness of the catalyst film is 5 nm-50 μm.

[0023] Furthermore, in S3, the catalyst is deposited in the high-pressure cavity in the form of a thin film;

[0024] Preferably, the thickness of the catalyst film is 5 nm-50 μm.

[0025] Furthermore, in S13, the molar ratio of H2 to the mixed gas is 5% to 95%.

[0026] Compared with the prior art, the present invention can achieve at least one of the following technical effects:

[0027] 1) The present invention's method for synthesizing a polymerized carbon monoxide (COH) energetic material (hereinafter abbreviated as p-COH) promotes the polymerization reaction of the polymerized COH energetic material using a catalyst (e.g., a noble metal such as palladium, platinum, ruthenium, rhodium, gold, or noble metal-supported copper oxide or ceria), thereby reducing the pressure required for the polymerization reaction of carbon monoxide and hydrogen. Compared to the polymerization reaction of carbon monoxide and hydrogen without the addition of a catalyst, the synthesis pressure of different p-COH crystalline phases (different crystalline phases refer to different products obtained at different pressures using the same raw materials) is reduced from the current 5-80 GPa to 3-60 GPa, a reduction of 2-20 GPa. For example, the synthesis pressure of recyclable p-COH-I is reduced from approximately 5-20 GPa to 3-9 GPa, the synthesis pressure of p-COH-II is reduced from approximately 7-30 GPa to 4-20 GPa, and the synthesis pressure of p-COH-III is reduced from approximately 20-80 GPa to 8-60 GPa. By reducing the synthesis pressure, the difficulty of preparing polymerized COH energetic materials can be greatly reduced, providing technical support for the mass production of polymerized COH energetic materials.

[0028] 2) The synthesis method of the polymerized COH energetic material of the present invention utilizes high-pressure loading to achieve the polymerization of a mixed gas of hydrogen and carbon monoxide; the p-COH prepared by this technology can achieve regulation of the carbon-hydrogen ratio of different components.

[0029] 3) Compared with pure polymerized carbon monoxide, the atomic hydrogen in the lattice of the p-COH energetic material prepared by the present invention has a certain passivating effect on the polymerized carbon monoxide material, thereby improving the stability of the polymerized COH energetic material. The material can be placed in the air for 1 to 2 days without deterioration, and its stability to light, heat, and water vapor is significantly improved.

[0030] 4) The improved polymerized COH energetic material (hereinafter abbreviated as p-COH') prepared by the present invention comprises polymerized CO and p-COH; wherein p-CO coats p-COH to form a composite structure with p-CO as the shell and p-COH as the core, and p-COH is formed by H-doping p-CO. The composite structure of p-COH' of the present invention improves the energy density and stability of p-CO. The density of the p-COH' of the present invention is approximately 2.3 to 6 g / cm 3 It is a high-energy-density material and a new type of material with high-energy performance. p-COH′ can be placed in the air for 2 to 5 days without deterioration. Its stability to light, heat, and water vapor is significantly improved, and it has broad application prospects in many fields.

[0031] Other features and advantages of the present invention will be described in the following description, and in part they may become apparent from the description or may be understood through implementation of the present invention. The purposes and other advantages of the present invention may be realized and obtained through the structures particularly pointed out in the written description and the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The drawings are only for purposes of illustrating particular embodiments and are not to be considered limiting of the present invention. Like reference numerals designate like components throughout the drawings.

[0033] Figure 1 This is a Raman spectrum of a H2 and CO mixed system under normal pressure conditions in Example 1-1 of the present invention;

[0034] Figure 2 This is a Raman spectrum of the 5 GPa, p-COH energetic material in Example 1-1 of the present invention;

[0035] Figure 3 This is a Raman spectrum of liquid CO and p-COH energetic materials as pressure changes in Example 1-1 of the present invention;

[0036] Figure 4 This is a diagram showing the effect of laser detonation of the p-COH-II′ energetic material in Example 1-2 of the present invention. DETAILED DESCRIPTION

[0037] The following is a further detailed description of a catalytic synthesis catalyst and synthesis method for polymerizing COH energetic materials in conjunction with specific examples. These examples are only for comparison and explanation purposes, and the present invention is not limited to these examples.

[0038] After in-depth research, the inventors applied a catalyst to the synthesis process of the polymerized COH energetic material in order to reduce the pressure required for the synthesis process of the polymerized COH energetic material, thereby reducing the pressure required for the synthesis of the polymerized COH energetic material.

[0039] The present invention provides an application of a catalyst in the synthesis of a polymerized COH energetic material. The catalyst can be a precious metal such as palladium, platinum, ruthenium, rhodium, gold, or a precious metal-loaded copper oxide, cerium dioxide, or other material. The application of the catalyst in the synthesis of the polymerized COH energetic material reduces the pressure required for the synthesis of the polymerized COH energetic material.

[0040] The present invention provides a method for synthesizing a polymerized COH energetic material, comprising the following steps:

[0041] S1. Loading hydrogen (H2) and carbon monoxide (CO) gas into a high-pressure chamber, and then sealing the high-pressure chamber; wherein hydrogen accounts for 5% to 95% of the mixed gas, and a catalyst is placed in the high-pressure chamber;

[0042] S2. Pressurize the hydrogen and carbon monoxide mixed gas in the high-pressure chamber, and maintain the target pressure for 5 minutes to several days (for example, 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, etc.) to prepare a polymerized COH material. Then slowly unload the pressure, open the high-pressure chamber, and obtain a polymerized COH energetic material (hereinafter abbreviated as p-COH).

[0043] It should be noted that the above-mentioned catalysts include precious metals such as palladium, platinum, ruthenium, rhodium, gold, and precious metal-loaded copper oxide, cerium dioxide and other materials.

[0044] Specifically, the catalyst is deposited in the high-pressure cavity in the form of a thin film.

[0045] It should be noted that the above-mentioned synthesis method of p-COH energetic materials is carried out in a high-pressure device, which can be a multi-sided top press (such as a six-sided top press), a two-sided top press (such as a Paris-Edinburgh (PE) press, a diamond anvil cell) or a ring press.

[0046] Specifically, the above S1 includes:

[0047] S11. Complete the preparation work for the pressurized accessories of the high-pressure device;

[0048] S12, assembling the pressurized accessories of the high-pressure device into the thermostat cavity, and sealing the thermostat cavity;

[0049] S13, loading a mixture of carbon monoxide and hydrogen into the high-pressure chamber, and then sealing the high-pressure chamber by adjusting the relative positions of an upper anvil and a lower anvil of the high-pressure device;

[0050] S14. Release the remaining carbon monoxide and hydrogen in the thermostat cavity and remove the pressurizing accessories of the high-pressure device.

[0051] In the above S11, the preparation work for the pressurized accessories of the high-pressure device includes:

[0052] S111. Select a matching gasket based on the anvil area of the high-pressure device and pre-press it to create an indentation at the center of the gasket.

[0053] S112, punching a circular hole at the center of the seal indentation, the circular hole serving as a high-pressure chamber for sample packaging and reaction;

[0054] S113, depositing a catalyst thin film on the upper anvil surface and the lower anvil surface of the high-pressure anvil respectively;

[0055] S114, fixing the gasket at the indentation position of the lower anvil surface of the high-pressure device;

[0056] S115. Close the high-pressure anvil and the gasket tightly, and then open them to a certain distance for packaging the hydrogen and carbon monoxide mixed gas.

[0057] In the above S111, the material of the gasket can be T301 stainless steel, a metal rhenium sheet, a metal tungsten sheet, or the like.

[0058] In the above S112, the gasket is punched by laser punching or mechanical punching.

[0059] In the above-mentioned S113, the catalyst can be deposited onto the surface of the anvil by magnetron sputtering in the form of a thin film. Considering that if the thickness of the catalyst film is too small, it is easy to fall off during the implementation process, and if the thickness of the catalyst film is too large, the catalytic effect is insufficient and the pressure required for polymerization is affected, the thickness of the catalyst film is controlled to be 5nm-50μm, for example, 5-80nm. To prevent oxidation or deterioration of the catalyst during the deposition process, the entire catalyst deposition process is completed in high-purity argon.

[0060] In the above S115, the distance between the high-pressure anvil and the gasket should not be too large. Preferably, the distance is 0.3-0.5 mm.

[0061] Specifically, in the above step S12, after the high-pressure device pressurized accessory is installed in the low-temperature thermostat cavity, the gap position of the high-pressure device pressurized accessory needs to be sealed; the use of conical filling blocks can effectively occupy the gap inside the low-temperature thermostat, thereby reducing the volume of carbon monoxide required to be liquefied.

[0062] Specifically, in the above S13, the amount of hydrogen in the mixed gas is too much, and the pressure required for the synthesis process is too high and difficult to achieve. Therefore, the molar ratio of hydrogen to the mixed gas is 5% to 95%.

[0063] Specifically, in the above S13, carbon monoxide and hydrogen are loaded into the high-pressure chamber by low-temperature liquefaction and / or high-pressure compression. The main steps include:

[0064] S131, close the thermostat outlet valve;

[0065] S132, pressurizing carbon monoxide and hydrogen into the high-pressure chamber, and compressing the mixture of gaseous carbon monoxide and hydrogen by a high-pressure pump to fill the high-pressure chamber and the thermostat;

[0066] S133. Apply a certain pressure to the high-pressure chamber through the external operating lever of the thermostat, lock the pressurized accessories of the high-pressure device, and achieve the encapsulation of carbon monoxide and hydrogen in the high-pressure chamber. Then close the carbon monoxide and hydrogen inlet valves and open the outlet valve.

[0067] Specifically, in the above S131-S133, temperature and pressure sensors are set in the thermostat cavity to monitor the temperature and pressure conditions inside the cavity in real time.

[0068] Specifically, in the above S132 and S133, the pressure required for high-pressure compression of carbon monoxide and hydrogen is 0.2 to 2 GPa.

[0069] Specifically, in the above S2, if the pressurization rate is too high, it is easy to generate a pressure gradient, which is not conducive to sample synthesis. Therefore, the pressurization rate is controlled to 0.5-2 GPa / min, and the target pressure is 3-80 GPa; different crystalline phases of p-COH energetic materials are prepared. The p-COH energetic material is solid and has a variety of appearances such as black, brown and transparent, with a density of 2.3 g / cm 3 ~6g / cm 3 .

[0070] Specifically, the p-COH energetic material obtained in S2 has good stability and can be placed in the air for 1 to 2 days without deterioration.

[0071] It should be noted that, in the above S2, the target pressure is related to the molar ratio of carbon monoxide to hydrogen. The greater the amount of hydrogen, the greater the target pressure.

[0072] It should be noted that in S2 above, while the raw materials are controlled to be the same, products with different crystalline phases can be obtained at different pressures. Hereinafter, the products with different crystalline phases are represented by p-COH-I, p-COH-II, and p-COH-III. Considering that the pressures required for synthesizing p-COH-I vary depending on the ratio of CO to H2 in the present invention, a controlled variable method is employed when analyzing the effects of the present invention: that is, when comparing the pressures required for the reactions, only the presence or absence of a catalyst is controlled, while other raw material ratios and product conditions are kept the same.

[0073] For example, in S2 above:

[0074] When the molar ratio of carbon monoxide to hydrogen is 9:1, if the final product is p-COH-I, the target pressure is 2 to 4 GPa (e.g., 2.5 GPa, 3 GPa, 3.5 GPa); if the final product is p-COH-II, the target pressure is 5 to 7 GPa (e.g., 5.5 GPa, 6 GPa, 6.5 GPa); if the final product is p-COH-III, the target pressure is 8 to 60 GPa (e.g., 15 GPa, 20 GPa, 25 GPa, 27 GPa, 30 GPa, 35 GPa, 37 GPa, 40 GPa, 45 GPa, 47 GPa, 50 GPa, 35 GPa, 57 GPa);

[0075] When the molar ratio of carbon monoxide to hydrogen is 1:1, if the final product is p-COH-I, the target pressure is 4 to 6 GPa (e.g., 4.5 GPa, 5 GPa, 5.5 GPa); if the final product is p-COH-II, the target pressure is 5 to 10 GPa (5.5 GPa, 6 GPa, 6.5 GPa, 7 GPa, 7.5 GPa, 8 GPa, 8.5 GPa, 9 GPa, 9.5 GPa); if the final product is p-COH-III, the target pressure is 15 to 60 GPa (e.g., 20 GPa, 25 GPa, 27 GPa, 30 GPa, 33 GPa, 35 GPa, 37 GPa, 40 GPa, 45 GPa, 47 GPa, 50 GPa, 55 GPa, 57 GPa);

[0076] When the molar ratio of carbon monoxide to hydrogen is 1:9, if the final product is p-COH-I, the target pressure is 7 to 9 GPa (e.g., 7.5 GPa, 8 GPa, 8.5 GPa, 9 GPa); if the final product is p-COH-II, the target pressure is 15 to 20 GPa (e.g., 15.5 GPa, 16 GPa, 16.5 GPa, 17 GPa, 17.5 GPa, 18 GPa, 18.5 GPa, 19 GPa, 19.5 GPa); if the final product is p-COH-III, the target pressure is 20 to 60 GPa (e.g., 25 GPa, 27 GPa, 30 GPa, 35 GPa, 40 GPa, 45 GPa, 47 GPa, 50 GPa, 55 GPa, 57 GPa).

[0077] Compared with the prior art, the synthesis method of the polymerized COH energetic material of the present invention promotes the polymerization reaction of the polymerized COH energetic material through the action of a catalyst (such as precious metals such as palladium, platinum, ruthenium, rhodium, gold, and precious metal-loaded copper oxide and cerium dioxide), thereby reducing the pressure required for the polymerization reaction of carbon monoxide and hydrogen. Compared with the polymerization reaction of carbon monoxide and hydrogen without adding a catalyst, the synthesis pressure of different crystalline phases of p-COH (different crystalline phases refer to different products obtained under different pressures with the same raw materials) is reduced from the existing 5 to 80 GPa to 3 to 60 GPa, a reduction of 2 to 20 GPa.

[0078] The p-COH energetic material obtained by the present invention is a high energy density material and a new type of material with high energy performance, and has broad application prospects in multiple fields.

[0079] Furthermore, in order to improve the stability of the p-COH energetic material, the synthesis method of the polymerized COH energetic material may further include the following steps:

[0080] S3, placing the p-COH energetic material prepared in S2 above into a high-pressure cavity; wherein the volume of the p-COH energetic material is 5% to 95% of the volume of the high-pressure cavity; wherein a catalyst is placed in the high-pressure cavity;

[0081] S4, liquefying the carbon monoxide gas to fill the high-pressure cavity in S3, and then sealing the high-pressure cavity;

[0082] S5. Pressurize the material in the high-pressure cavity and maintain the target pressure for a period of time (e.g., 15 minutes to 10 days). Then, slowly unload the pressure and open the high-pressure cavity to obtain an improved p-COH energetic material (hereinafter, for distinction, this improved p-COH energetic material will be abbreviated as p-COH′).

[0083] Specifically, the above S3 includes the following main steps:

[0084] S31. Complete the preparation work for the pressurized accessories of the high-pressure device;

[0085] S32, cutting the p-COH material obtained in S2 into 5% to 95% of the volume of the high-pressure cavity;

[0086] S33, placing the p-COH material cut in step S32 into the high-pressure cavity;

[0087] S34. Close the high-pressure anvil and the gasket tightly, and then open them a certain distance for carbon monoxide packaging.

[0088] In the above S31, the high-pressure device includes a multi-sided top press (such as a six-sided top press), a two-sided top press (such as a Paris-Edinburgh (PE) press, a diamond anvil cell) and an annular press.

[0089] In the above step S31, the preparation work for the pressurized accessories of the high-pressure device is the same as that in step S11.

[0090] In the above S4, carbon monoxide gas is loaded into the high-pressure chamber by low-temperature liquefaction or high-pressure compression. The specific steps are as follows:

[0091] S41. Assemble the pressurized accessories of the high-pressure device into the thermostat cavity and seal the thermostat;

[0092] S42, introducing carbon monoxide gas into the thermostat;

[0093] S43. Close the carbon monoxide outlet valve: (1) cool the thermostat together with the introduced carbon monoxide gas to a temperature range between the melting point and boiling point of carbon monoxide, so that the carbon monoxide gas gradually liquefies and fills the high-pressure chamber and thermostat of the high-pressure device; or (2) compress the gaseous carbon monoxide by a high-pressure pump to fill the high-pressure chamber and thermostat;

[0094] S44. Apply a certain pressure to the pressurized attachment of the high-pressure device through the external operating lever of the thermostat to lock the high-pressure device so that the carbon monoxide is encapsulated in the high-pressure chamber. Then, close the carbon monoxide inlet valve and open the outlet valve.

[0095] S45. Increase the temperature or turn off the high-pressure pump to allow the remaining carbon monoxide in the thermostat to gradually evaporate and be discharged from the thermostat, and then remove the pressurized accessories of the high-pressure device.

[0096] In the above S41-S45, temperature and pressure sensors are set in the thermostat cavity to monitor the temperature and pressure conditions inside the cavity in real time.

[0097] In the above S43, the pressure required for high-pressure compression of carbon monoxide gas is 0.2 to 1 GPa.

[0098] In the above step S44, the pressure required for encapsulating the liquid carbon monoxide is 0.2-1 GPa.

[0099] Specifically, in the above S4, the liquid carbon monoxide in the high-pressure chamber accounts for 5% to 95% of the volume of the high-pressure chamber.

[0100] Specifically, in the above S5, the pressurization rate is 0.5 to 2 GPa / min, and the target pressure is 3 to 80 GPa (as the target pressure increases, p-COH-I′, p-COH-II′, and p-COH-III′ crystal phases are formed respectively).

[0101] Specifically, in the above S5:

[0102] If the final product is p-COH-I′, the target pressure is 3 to 9 GPa (e.g., 3.5 GPa, 4 GPa, 4.5 GPa, 5 GPa, 5.5 GPa, 6 GPa, 6.5 GPa, 7 GPa, 7.5 GPa, 8 GPa, 8.5 GPa, 9 GPa);

[0103] If the final product is p-COH-II′, the target pressure is 4-20 GPa (e.g., 4.5 GPa, 5 GPa, 6 GPa, 7 GPa, 8 GPa, 9 GPa, 10 GPa, 11 GPa, 12 GPa, 13 GPa, 14 GPa, 15 GPa, 16 GPa, 17 GPa, 18 GPa, 19 GPa);

[0104] If the final product is p-COH-III′, the target pressure is 25-60 GPa (e.g., 30 GPa, 35 GPa, 40 GPa, 45 GPa, 50 GPa, 55 GPa).

[0105] Specifically, in the above S5, the p-COH′ samples of different crystalline phases are prepared as solids with various appearances such as black, brown, and red, and a density of 2 g / cm 3 ~6g / cm 3 .

[0106] Specifically, in the above S5, the p-COH′ energetic material obtained is composed of three elements: carbon, hydrogen, and oxygen; p-COH′ is a metastable material, and its structure contains a three-dimensional network structure, a two-dimensional layered structure, and a one-dimensional chain structure formed by CC, C=C, OO, CH, OH, and atomic H; the p-COH′ material is prepared according to a two-step method, and its structural characteristics are: the first step is to prepare p-COH, and the second step is to achieve the coating of p-COH with p-CO, forming a composite structure with p-CO as the shell and p-COH as the core.

[0107] Specifically, in the above S5, the p-COH′ energetic material obtained is a block solid with various appearances such as black, brown, red and transparent, and a density of 2.3 g / cm 3 ~6g / cm 3 The specific density is determined by the ratio of carbon to hydrogen in the polymer. The resulting p-COH' energetic material has good stability and can be placed in air for 2 to 5 days without deterioration.

[0108] Specifically, in the above-mentioned synthesis method of the p-COH energetic material, Raman spectroscopy can be used to monitor the physical state transformation process of the sample inside the high-pressure cavity.

[0109] Example 1-1

[0110] This embodiment provides a method for synthesizing a polymerized COH energetic material, comprising:

[0111] S1. Loading hydrogen and carbon monoxide gases into a high-pressure chamber, and then sealing the high-pressure chamber; wherein the molar ratio of hydrogen to carbon monoxide is 1:1; wherein the thickness of the palladium film on the anvil surface of the high-pressure chamber is 10 nm;

[0112] S2. Pressurize the hydrogen and carbon monoxide gases in the high-pressure chamber until they reach 5 GPa and maintain for 10 minutes to prepare the p-COH material. Then slowly unload the pressure and open the high-pressure chamber to obtain the p-COH-II energetic material.

[0113] Specifically, in S1, the hydrogen and carbon monoxide mixed gas is loaded into the high-pressure chamber by high-pressure inflation. The main steps include:

[0114] S11. Complete the preparation work for the pressurized accessories of the high-pressure device;

[0115] S12, assembling the pressurized accessories of the high-pressure device into the constant temperature cavity, and sealing the constant temperature cavity;

[0116] S13, introducing a mixture of carbon monoxide and hydrogen in a molar ratio of 1:1 into the constant temperature chamber, and sealing it by high pressure loading and pressurization operation;

[0117] S14. Release the remaining carbon monoxide and hydrogen in the thermostat cavity and remove the pressurizing accessories of the high-pressure device.

[0118] In the above S11, the preparation work for the pressurized accessories of the high-pressure device includes:

[0119] S111, pre-pressing the gasket using a diamond anvil so that an indentation appears at its center;

[0120] S112, punch a hole at the center of the gasket indentation;

[0121] S113, depositing a metal palladium film on the upper anvil surface and the lower anvil surface of the high-pressure anvil, respectively, wherein the thickness of the metal palladium film is 10 nm;

[0122] S114, fixing the gasket at the indentation position of the lower anvil surface;

[0123] S115. Tighten the upper anvil, the sealing gasket, and the lower anvil, and then open them by a certain distance (0.5 mm) for packaging the hydrogen and carbon monoxide mixed gas.

[0124] In the above S111, the material of the gasket is T301 stainless steel.

[0125] In the above S112, the gasket is punched by laser.

[0126] Specifically, in step S12, after the high-pressure device pressurized accessory is installed in the cryostat cavity, the gap in the high-pressure device pressurized accessory needs to be sealed. Using a conical filling block can effectively occupy the gap inside the cryostat, thereby reducing the volume of carbon monoxide required to be liquefied.

[0127] In the above S13, the pressure used to seal the mixed gas of hydrogen and carbon monoxide is 500 MPa.

[0128] In the above S2, the pressurization rate is 2 GPa / min, and the prepared p-COH-II energetic material is bright black with a density of about 2.7 g / cm 3 .

[0129] Example 1-2

[0130] This embodiment provides a method for synthesizing a polymerized COH energetic material, comprising:

[0131] S3. Place the p-COH-II energetic material of Example 1-1 into a high-pressure chamber; wherein the volume of the p-COH-II material is 80% of the volume of the high-pressure chamber; and the thickness of the palladium film on the anvil surface of the high-pressure chamber is 10 nm;

[0132] S4, liquefy the carbon monoxide gas and fill the high-pressure cavity of S3, and then seal the high-pressure cavity;

[0133] S5. Pressurize the material in the high-pressure cavity until it reaches 5 GPa, maintain it for 20 minutes, then slowly unload the pressure and open the high-pressure cavity to obtain the p-COH-II′ energetic material.

[0134] Specifically, in the above S4, the carbon monoxide gas is loaded into the pressurizing attachment of the high-pressure device by low-temperature liquefaction. The main steps include:

[0135] S41. Assemble the pressurized accessories of the high-pressure device into the thermostat cavity and seal the thermostat;

[0136] S42, introducing carbon monoxide gas into the thermostat;

[0137] S43, cooling the thermostat together with the introduced carbon monoxide gas to a temperature range between the melting point and boiling point of carbon monoxide, so that the carbon monoxide gas gradually liquefies and fills the high-pressure chamber and the thermostat, and then closing the carbon monoxide inlet and outlet valves;

[0138] S44. Apply a certain pressure through the external operating lever of the thermostat to lock the pressurized attachment of the high-pressure device, thereby encapsulating the carbon monoxide liquid in the high-pressure chamber;

[0139] S45. Increase the temperature to allow the remaining carbon monoxide liquid in the thermostat to gradually vaporize and discharge from the thermostat, and then remove the pressurized accessories of the high-pressure device.

[0140] Specifically, in the above S41, the sealing process is completed by closing and tightening the connecting bolts between the thermostat body and the thermostat top cover.

[0141] Specifically, in the above S42, the assembled thermostat is connected to the gas line, and the gas outlet valve of the thermostat is opened; the pressure reducing valve of the carbon monoxide cylinder and the gas valve of the thermostat are used to control the flow rate of gaseous carbon monoxide so that it slowly enters the cavity of the thermostat; ventilation is carried out for about 5 minutes to discharge the air in the thermostat cavity; the bolts of the high-pressure device are loosened using the operating lever on the thermostat to create a gap between the upper anvil and the gasket, and the original gas in the high-pressure cavity is discharged with the help of the introduced carbon monoxide gas; and then the gas outlet valve of the thermostat is closed.

[0142] Specifically, in the above S43, the thermostat is first placed in a liquid nitrogen environment to cool the thermostat equipment; the temperature and pressure state of the incoming gas are monitored in real time by the temperature and pressure sensors in the thermostat; when the temperature inside the thermostat drops below the boiling point of carbon monoxide gas, the gaseous carbon monoxide begins to gradually liquefy; since the liquefaction of the gas releases a large amount of heat, the local environment undergoes significant changes and the air pressure fluctuates violently; after cooling for 20-40 minutes, the temperature sensor shows that the boiling point of liquid nitrogen in the thermostat is around 77K, at which time the gaseous carbon monoxide is liquefied in large quantities; continue to wait for 20 to 30 minutes, and the liquid carbon monoxide can fill the entire low-temperature thermostat.

[0143] In the above S44, the pressure required to encapsulate the liquid carbon monoxide is 500 MPa.

[0144] Specifically, in S45 , the thermostat's air inlet valve is closed, the main valve of the gas cylinder is closed, and the cooling device below the thermostat is slowly removed to gradually heat the thermostat. The thermostat's air outlet valve is then opened to slowly discharge the carbon monoxide. Because liquid carbon monoxide rapidly vaporizes when the thermostat's temperature approaches the boiling point of carbon monoxide, a large amount of gas is generated. The air outlet valve must be controlled to slowly discharge the exhaust gas. Once the temperature reaches room temperature and the pressure inside the thermostat returns to normal, the high-pressure device's pressurization accessories can be removed.

[0145] In the above S4, the volume ratio of liquid carbon monoxide to p-COH-II material in the high-pressure chamber is 1:4.

[0146] In the above S5, the pressure increase rate is 2 GPa / min. The prepared p-COH-II′ sample is a black solid with a density of about 2.6 g / cm 3 Without the addition of a catalyst, the synthesis pressure of the p-COH-II sample was 7 GPa, as shown in Comparative Example 1-1. Without the addition of a catalyst, the synthesis pressure of the p-COH-II′ sample was 7 GPa, as shown in Comparative Example 1-2. In contrast, the synthesis pressures of p-COH-II and p-COH-II′ decreased from 7 GPa to 5 GPa, a decrease of 2 GPa.

[0147] During the synthesis of p-COH-II materials, Raman spectroscopy was used to monitor the physical state transformation process of the samples, such as Figure 1 As shown, it can be clearly seen through Raman spectroscopy test that 4200 cm -1 is the Raman peak of H2, 2140 cm -1 Nearby is the Raman peak of CO; at 5GPa( Figure 2 ), the Raman peaks of H2 and CO disappear, and at 1600 cm -1The C=O double bond Raman peak appeared near the p-COH-II material, indicating the formation of p-COH-II material. After filling the high-pressure cavity of the built-in p-COH-II material with CO, a peak at 2140 cm was detected. -1 As the pressure gradually increases, the Raman peak of CO disappears at 5 GPa, and the p-CO Raman peak appears, indicating the formation of p-COH-II′ material. Figure 4 This is the laser detonation effect diagram of p-COH-II′.

[0148] Example 2-1

[0149] This embodiment provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Example 1-1, except that:

[0150] In S1, the molar ratio of hydrogen to carbon monoxide is 1:2, and the thickness of the gold film on the anvil surface of the high-pressure chamber is 10 nm;

[0151] In S115, the distance of the further opening of the certain distance is 0.5 mm.

[0152] In S13, the pressure used to seal the hydrogen and carbon monoxide mixture is 300 MPa;

[0153] In S2, the pressurization rate is 1 GPa / min, the target pressure is 3 GPa, and it is maintained for 30 min;

[0154] In S2, the prepared p-COH-I energetic material is bright black and has a density of approximately 2.4 g / cm 3 .

[0155] As shown in Comparative Example 2-1, when no catalyst is added, the synthesis pressure of the p-COH-I sample is 5 GPa. In contrast, the synthesis pressure of p-COH-I is reduced from 5 GPa to 3 GPa, a decrease of 2 GPa.

[0156] Example 2-2

[0157] This embodiment provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Embodiment 1-2, except that:

[0158] In S3, the p-COH-I energetic material of Example 2-1 is used, and the volume of the p-COH-I energetic material is 20% of the volume of the high-pressure cavity.

[0159] In S44, the pressure required to encapsulate liquid carbon monoxide is 300 MPa.

[0160] In S4, the volume ratio of liquid carbon monoxide to p-COH-I in the high-pressure chamber is 4:1.

[0161] In S5, the pressure increase rate is 2 GPa / min; the target pressure is 3 GPa, which is maintained for 25 minutes;

[0162] The p-COH-I′ sample prepared in S5 was a black solid with a density of approximately 2.3 g / cm 3 .

[0163] In the synthesis of p-COH-I′ energetic materials, the formation process of p-COH-I and p-COH-I′ can be detected by Raman spectroscopy, which will not be described here.

[0164] As shown in Comparative Example 2-2, when no catalyst is added, the synthesis pressure of the p-COH-I′ sample is 5 GPa. In contrast, the synthesis pressure of p-COH-I′ is reduced from 5 GPa to 3 GPa, a decrease of 2 GPa.

[0165] Example 3-1

[0166] This embodiment provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Example 1, except that:

[0167] In S1, the molar ratio of hydrogen to carbon monoxide is 1:4, and the thickness of the cerium oxide film on the anvil surface of the high-pressure chamber is 20 nm;

[0168] In S115, the distance of the further opening of the certain distance is 0.5 mm.

[0169] In S13, the pressure used to seal the hydrogen and carbon monoxide mixed gas is 200 MPa;

[0170] In S2, the pressurization rate is 1 GPa / min, the target pressure is 10 GPa, and it is maintained for 20 min;

[0171] In S2, the prepared p-COH-III energetic material is light yellow and has a density of about 5.3 g / cm 3 .

[0172] During the synthesis of p-COH-III material, its formation process can be detected using Raman spectroscopy, which will not be described in detail here.

[0173] As shown in Comparative Example 3-1, when no catalyst is added, the synthesis pressure of p-COH-III is 20 GPa. In contrast, the synthesis pressure of p-COH-III is reduced from 20 GPa to 10 GPa, a decrease of 10 GPa.

[0174] Example 3-2

[0175] This embodiment provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Embodiment 1-2, except that:

[0176] In S3, the p-COH-III energetic material of Example 3-1 is used, and the volume of the p-COH-III energetic material is 80% of the volume of the high-pressure cavity.

[0177] In S44, the pressure required to encapsulate the liquid carbon monoxide is 200 MPa.

[0178] In S4, the volume ratio of liquid carbon monoxide to p-COH-III energetic material in the high-pressure chamber is 1:4.

[0179] In S5, the pressure increase rate is 1 GPa / min; the target pressure is 40 GPa, which is maintained for 20 minutes;

[0180] The p-COH-III′ sample prepared in S5 was a black solid with a density of approximately 4.2 g / cm 3 .

[0181] During the synthesis of the p-COH-III′ material, its formation process can be detected using Raman spectroscopy, which will not be described in detail here.

[0182] As shown in Comparative Example 3-2, when no catalyst is added, the synthesis pressure of p-COH-III′ is 60 GPa. In contrast, the synthesis pressure of p-COH-III is reduced from 60 GPa to 40 GPa, a decrease of 20 GPa.

[0183] Example 4-1

[0184] This embodiment provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Example 1, except that:

[0185] In S1, the molar ratio of hydrogen to carbon monoxide is 5:1, and the catalyst on the anvil surface of the high-pressure chamber is a platinum and copper oxide film with a thickness of 20 nm;

[0186] In S115, the distance in the certain distance is opened again to 0.5 mm;

[0187] In S13, the pressure used to seal the hydrogen and carbon monoxide mixture is 800 MPa;

[0188] In S2, the pressurization rate is 2 GPa / min, the target pressure is 25 GPa, and it is maintained for 60 min;

[0189] In S2, the prepared p-COH-III sample was bright black and had a density of approximately 5 g / cm 3 .

[0190] During the synthesis of p-COH-III material, its formation process was detected using Raman spectroscopy, which will not be described in detail here.

[0191] As shown in Comparative Example 4-1, when no catalyst is added, the synthesis pressure of p-COH-III is 30 GPa. In this embodiment, the synthesis pressure of p-COH-III is reduced from 30 GPa to 25 GPa, a decrease of 5 GPa.

[0192] Example 4-2

[0193] This embodiment provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Embodiment 1-2, except that:

[0194] In S3, the p-COH-III energetic material of Example 4-1 is used, and the volume of the p-COH-III energetic material is 90% of the volume of the high-pressure cavity.

[0195] In S44, the pressure required to encapsulate liquid carbon monoxide is 800 MPa.

[0196] In S4, the volume ratio of liquid carbon monoxide to p-COH-III energetic material in the high-pressure chamber is 1:9.

[0197] In S5, the pressure increase rate is 2 GPa / min; the target pressure is 60 GPa, which is maintained for 30 minutes;

[0198] In S5, the prepared p-COH-III′ energetic material is a black solid with a density of about 4.6 g / cm 3 .

[0199] During the synthesis of the p-COH-III′ material, the formation process was detected using Raman spectroscopy, which will not be described in detail here.

[0200] As shown in Comparative Example 4-2, when no catalyst is added, the synthesis pressure of p-COH-III′ is 80 GPa. In this embodiment, the synthesis pressure of p-COH-III′ is reduced to 60 GPa, a decrease of 20 GPa.

[0201] In order to illustrate the beneficial effect of adding a catalyst in the present invention on reducing the reaction pressure, the inventors conducted the following experiments for comparison.

[0202] Comparative Example 1-1

[0203] This comparative example provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Example 1-1, except that:

[0204] In S1, no palladium film is provided on the anvil surface of the high-pressure chamber.

[0205] In S2, the pressurization rate is 2 GPa / min, the target pressure is 7 GPa, and it is maintained for 30 min;

[0206] In S2, the prepared p-COH-II energetic material is bright black and has a density of approximately 2.7 g / cm 3 .

[0207] Comparative Example 1-1

[0208] This comparative example provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Example 1-2, except that:

[0209] In S3, the p-COH-II energetic material of Comparative Example 1-1 is used.

[0210] In S44, the pressure required to encapsulate liquid carbon monoxide is 500 MPa.

[0211] In S5, the pressure increase rate is 2 GPa / min; the target pressure is 7 GPa, which is maintained for 30 minutes;

[0212] In S5, the prepared p-COH-II′ energetic material is a black solid with a density of about 2.6 g / cm 3 .

[0213] Comparative Example 2-1

[0214] This comparative example provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Example 2-1, except that:

[0215] In S1, no gold film is provided on the anvil surface of the high-pressure chamber;

[0216] In S13, the pressure used to seal the hydrogen and carbon monoxide mixture is 300 MPa;

[0217] In S2, the pressurization rate is 1 GPa / min, the target pressure is 5 GPa, and it is maintained for 30 min;

[0218] The p-COH-I sample prepared in S2 is light yellow and has a density of approximately 2.3 g / cm 3 .

[0219] Comparative Example 2-2

[0220] This comparative example provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Example 2-2, except that:

[0221] In S3, the p-COH-I energetic material of Comparative Example 2-1 is used, and the volume of the p-COH-I energetic material is 80% of the volume of the high-pressure cavity.

[0222] In S44, the pressure required to encapsulate liquid carbon monoxide is 200 MPa.

[0223] In S5, the pressure increase rate is 1 GPa / min; the target pressure is 5 GPa, which is maintained for 20 minutes;

[0224] The p-COH-I′ sample prepared in S5 was a light yellow solid with a density of approximately 2.2 g / cm 3 .

[0225] Comparative Example 3-1

[0226] This comparative example provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Example 3-1, except that:

[0227] In S1, no cerium oxide film is provided on the anvil surface of the high-pressure chamber;

[0228] In S2, the pressurization rate is 1 GPa / min, the target pressure is 20 GPa, and it is maintained for 20 min;

[0229] In S2, the prepared p-COH-III energetic material is light yellow and has a density of about 5.3 g / cm 3 .

[0230] Comparative Example 3-2

[0231] This comparative example provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Example 3-2, except that:

[0232] In S3, the p-COH-III energetic material of Comparative Example 3-1 is used, and the volume of the p-COH-III energetic material pH / CO material is 80% of the volume of the high-pressure chamber;

[0233] In S44, the pressure required to encapsulate liquid carbon monoxide is 200 MPa;

[0234] In S4, the volume ratio of liquid carbon monoxide to pH / CO material in the high-pressure chamber is 1:4;

[0235] In S5, the pressure increase rate is 1 GPa / min; the target pressure is 60 GPa, which is maintained for 20 minutes;

[0236] In S5, the prepared p-COH-III′ energetic material is a black solid with a density of about 4.2 g / cm 3 .

[0237] Comparative Example 4-1

[0238] This comparative example provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Example 4-1, except that:

[0239] In S1, no platinum and copper oxide films are provided on the anvil surface of the high-pressure chamber;

[0240] In S13, the pressure used to seal the hydrogen and carbon monoxide mixture is 1 GPa;

[0241] In S2, the pressurization rate is 2 GPa / min, the target pressure is 30 GPa, and it is maintained for 60 min;

[0242] In S2, the prepared p-COH-III energetic material is bright black and has a density of about 5 g / cm 3 .

[0243] Comparative Example 4-2

[0244] This comparative example provides a method for synthesizing a polymerized COH energetic material. The steps are substantially the same as those in Example 4-2, except that:

[0245] In S3, the p-COH-III energetic material of Comparative Example 4-1 is used, and the volume of the p-COH-III energetic material is 90% of the volume of the high-pressure cavity;

[0246] In S44, the pressure required to encapsulate liquid carbon monoxide is 1 GPa;

[0247] In S4, the volume ratio of liquid carbon monoxide to p-COH-III energetic material in the high-pressure chamber is 1:9;

[0248] In S5, the pressure increase rate is 2 GPa / min; the target pressure is 80 GPa, which is maintained for 30 minutes;

[0249] The p-COH-III′ sample prepared in S5 was a black solid with a density of approximately 4.6 g / cm 3 .

[0250] Specifically, the p-COH-I, p-COH-II and p-COH-III energetic materials obtained in Examples 1-1, 2-1, 3-1 and 4-1 of the present invention can be stably stored in the air for 1 to 2 days. Compared with pure p-CO, which can only be stably stored for a few hours in the air, the p-COH material of the present invention has good stability. Specifically, the p-COH-I′, p-COH-II′ and p-COH-III′ energetic materials obtained in Examples 1-2, 2-2, 3-2 and 4-2 of the present invention can be stably stored in the air for 2 to 5 days, have good stability, and their stability to light, heat and water vapor is significantly improved.

[0251] As can be seen from the examples and comparative examples of the present invention, by adding a catalyst to the synthesis process of the polymerized COH energetic material, the present invention effectively reduces the required pressure for the synthesis of the polymerized COH energetic material from the current 5-80 GPa to 3-60 GPa, thus simplifying the preparation of the polymerized COH energetic material and providing technical support for the mass production of the polymerized COH energetic material.

[0252] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed by the present invention should be covered by the scope of protection of the present invention.

Claims

1. Use of a catalyst in the synthesis of polymerized COH energetic materials, characterized in that: The catalyst is a noble metal or noble metal-supported copper oxide or cerium dioxide material, and the catalyst is used in the synthesis of polymerized COH energetic materials, thereby reducing the pressure required for the synthesis of polymerized COH energetic materials; The noble metal is palladium, platinum, ruthenium, rhodium or gold; The synthesis of the polymerized COH energetic material includes loading H2 and CO gases into a high-pressure cavity and then sealing the high-pressure cavity; wherein a catalyst is placed in the high-pressure cavity; the catalyst is deposited into the high-pressure cavity in the form of a thin film; the thickness of the catalyst film is 5nm-50μm.

2. A method for synthesizing a polymeric COH energetic material, characterized in that: The synthesis method adds a catalyst to the high-pressure reaction to reduce the pressure required for synthesizing the polymerized COH energetic material; the catalyst is a noble metal or a noble metal-loaded copper oxide or cerium dioxide material; the noble metal is palladium, platinum, ruthenium, rhodium or gold; The synthesis method comprises the following steps: S1. Loading H2 and CO gases into a high-pressure chamber, and then sealing the high-pressure chamber; wherein a catalyst is placed in the high-pressure chamber; S2, pressurizing the H2 and CO gases in the high-pressure chamber, maintaining the target pressure for a period of time, then unloading the pressure and opening the high-pressure chamber to obtain a polymerized COH energetic material; In the above-mentioned S1, the catalyst is deposited in the high-pressure cavity in the form of a thin film; the thickness of the catalyst thin film is 5nm-50μm.

3. The synthesis method according to claim 2, characterized in that Said S1 comprises: S11. Complete the preparation work for the pressurized accessories of the high-pressure device; S12, assembling the pressurized accessories of the high-pressure device into the thermostat cavity, and sealing the thermostat cavity; S13, loading a mixture of carbon monoxide and hydrogen into the high-pressure chamber, and then sealing the high-pressure chamber by adjusting the relative positions of an upper anvil and a lower anvil of the high-pressure device; S14. Release the remaining carbon monoxide and hydrogen in the thermostat cavity and remove the pressurizing accessories of the high-pressure device.

4. The synthesis method according to claim 2, characterized in that Also includes: S3, placing the polymerized COH energetic material obtained in S2 into a high-pressure cavity; wherein a catalyst is placed in the high-pressure cavity; S4, liquefying the carbon monoxide gas to fill the high-pressure cavity in S3, and then sealing the high-pressure cavity; S5. Pressurize the material in the high-pressure cavity in S4, maintain the target pressure, and then unload the pressure and open the high-pressure cavity to obtain the improved polymerized COH energetic material.

5. The synthesis method according to claim 2, characterized in that In the above-mentioned S1, the thickness of the catalyst film is 10 nm-50 μm.

6. The synthesis method according to claim 4, characterized in that In the above-mentioned S3, the catalyst is deposited in the high-pressure cavity in the form of a thin film; the thickness of the catalyst thin film is 5nm-50μm.

7. The synthesis method according to any one of claims 3 to 6, characterized in that In the step S13, the molar ratio of H2 to the mixed gas is 5% to 95%.

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