Atomic polymerized nitrogen material and preparation method thereof

Abstract

The present invention discloses an atomically polymerized nitrogen material and a preparation method thereof, belonging to the technical field of energetic materials, and solves one of the following problems: (1) the relatively harsh conditions for synthesizing cg-PN; and (2) the low content of cg-PN prepared by the prior art. The preparation method of the present invention obtains the atomically polymerized nitrogen material by directly quenching an azide compound from a high temperature to room temperature under high pressure. The cg-PN prepared by the preparation method of the present invention has high yield and can be recovered under conventional conditions, and has potential application value in the field of energetic materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of energetic materials, and in particular relates to an atomic polymerized nitrogen material and a preparation method thereof. Background Art

[0002] The nitrogen-nitrogen triple bond (N≡N) in nitrogen molecules (N≡N) has a high average bond energy and high chemical stability. The average bond energy of the nitrogen-nitrogen double bond (N=N) decreases in sequence with the average bond energy of the nitrogen-nitrogen single bond (N–N). When nitrogen molecules (N≡N) are converted to nitrogen-nitrogen single bonds (N–N), a polymerized nitrogen material is formed. This conversion process can store a large amount of energy. Conversely, when these all-nitrogen compounds decompose under suitable conditions, the polymerized nitrogen bound by nitrogen-nitrogen single bonds can be converted into stable nitrogen-nitrogen triple-bonded molecules (N≡N), releasing up to approximately 800 kJ / mol of energy in this process. Therefore, all-nitrogen compounds composed solely of nitrogen-nitrogen single bonds theoretically possess extremely high energy storage and release capabilities and are widely considered to be high-energy-density materials with potential applications.

[0003] At present, the synthesis of polymeric nitrogen usually requires preparation under conditions of high temperature and high pressure or the addition of a large amount of auxiliary substances, and the preparation conditions are harsh. Summary of the Invention

[0004] In view of the above analysis, the present invention aims to provide an atomic polymerized nitrogen material and a preparation method thereof to solve one of the following technical problems: the conditions for synthesizing atomic polymerized nitrogen material (i.e., cg-PN) are relatively harsh; the prepared cg-PN content is low.

[0005] The purpose of the present invention is mainly achieved through the following technical solutions:

[0006] In one aspect, the present invention provides a method for preparing an atomically polymerized nitrogen material, wherein the atomically polymerized nitrogen material is obtained by directly quenching an azide compound from a high temperature to room temperature under high pressure.

[0007] Furthermore, the pressure range of high pressure is 2GPa to 10GPa.

[0008] Furthermore, the high temperature range is 150°C to 550°C.

[0009] Furthermore, the azide compound includes one or more of KN3, NaN3, LiN3 and NH4N3.

[0010] Furthermore, when the azide compound is NH4N3, the high temperature is 150-250°C.

[0011] Furthermore, when the azide compound is LiN3, the high temperature is 150-260°C.

[0012] Furthermore, when the azide compound is NaN3, the high temperature is 250-350°C.

[0013] Furthermore, when the azide compound is KN3, the high temperature is 250-550°C.

[0014] Furthermore, the preparation method further comprises: quenching to room temperature and then releasing pressure to obtain the atomically polymerized nitrogen material.

[0015] The present invention also provides an atomic polymerized nitrogen material, which is prepared by the above preparation method.

[0016] Compared with the prior art, the present invention can achieve at least one of the following technical effects:

[0017] 1) In the preparation method of the present invention, the azide compound is directly quenched from high temperature to room temperature under high pressure, providing two degrees of freedom, pressure and temperature, to produce an atomically polymerized nitrogen material. This preparation method reduces the preparation conditions of the atomically polymerized nitrogen material from 110 GPa to 2 GPa to 10 GPa, significantly reducing the difficulty of synthesis.

[0018] 2) The preparation method of the present invention produces a higher cg-PN content. For example, in the Raman spectrum, the Raman peak corresponding to the A mode of cg-PN is 1 to 7 times that of the characteristic peak of the raw material. Furthermore, the cg-PN material prepared by this method is not limited to maintaining its stability under high-pressure conditions. Even after the high pressure applied during the synthesis process is released, the cg-PN can still maintain its structure and properties under normal pressure, breaking through the limitation of traditional technologies that polymerized nitrogen can only exist under extreme high pressure. This feature makes the material more operational and flexible in practical applications, and can open up new application prospects in fields such as energy storage and high-energy-density energetic materials.

[0019] 3) The method of the present invention achieves a fast cg-PN synthesis reaction rate, which can improve synthesis efficiency. The method of the present invention has good operability and industrial application prospects, and is expected to bring new breakthroughs in the preparation of high-energy-density energetic materials and provide important technical support for the research and development of energy materials.

[0020] 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

[0021] 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.

[0022] Figure 1 is the Raman spectrum of cg-PN of Example 1 of the present invention;

[0023] Figure 2 is the Raman spectrum of cg-PN of Example 2 of the present invention;

[0024] Figure 3 is the Raman spectrum of cg-PN of Example 3 of the present invention;

[0025] Figure 4 is the Raman spectrum of cg-PN of Example 4 of the present invention;

[0026] Figure 5 is the Raman spectrum of cg-PN of Example 5 of the present invention;

[0027] Figure 6 is the Raman spectrum of cg-PN of Example 6 of the present invention;

[0028] Figure 7 is the Raman spectrum of cg-PN of Example 7 of the present invention;

[0029] Figure 8 is the Raman spectrum of cg-PN of Example 8 of the present invention;

[0030] Figure 9 is the Raman spectrum of cg-PN of Example 9 of the present invention;

[0031] Figure 10 is the Raman spectrum of cg-PN of Example 10 of the present invention;

[0032] Figure 11 is the Raman spectrum of cg-PN of Example 11 of the present invention;

[0033] Figure 12 is the Raman spectrum of cg-PN of Example 12 of the present invention;

[0034] Figure 13 This is the Raman spectrum of KN3 of Comparative Example 1 of the present invention;

[0035] Figure 14 is the Raman spectrum of the unknown phase of Comparative Example 2 of the present invention;

[0036] Figure 15 This is the Raman spectrum of KN3 of Comparative Example 3 of the present invention;

[0037] Figure 16 is the Raman spectrum of the unknown phase of Comparative Example 4 of the present invention;

[0038] Figure 17 is the Raman spectrum of the unknown phase of Comparative Example 5 of the present invention; DETAILED DESCRIPTION

[0039] The following is a further detailed description of an atomic polymerized nitrogen material and its preparation method in conjunction with specific examples. These examples are only for comparison and explanation purposes, and the present invention is not limited to these examples.

[0040] The present invention provides a method for preparing an atomically polymerized nitrogen material. The method comprises directly quenching an azide compound from a high temperature to room temperature under high pressure to obtain the atomically polymerized nitrogen material.

[0041] Specifically, the above-mentioned azide compound includes one or more of KN3, NaN3, LiN3 and NH4N3.

[0042] Specifically, the pressure range of the high pressure is 2 GPa to 10 GPa. For example, the pressure of the high pressure is 2 GPa, 3 GPa, 4 GPa, 5 GPa, 6 GPa, 7 GPa, 8 GPa, and 9 GPa.

[0043] Specifically, the high temperature range is 150°C to 550°C, for example, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, and 550°C.

[0044] Specifically, the preparation method of the above-mentioned atomic polymerized nitrogen material includes the following steps:

[0045] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0046] S2. Pressurize the raw material until it reaches the target pressure (i.e., high pressure), then heat it to the target temperature (i.e., high temperature), and maintain the pressure and temperature;

[0047] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0048] It should be noted that in S1, the material of the inert metal cylinder is tantalum, stainless steel, gold, platinum, etc. The material of the inert metal cylinder does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0049] It should be noted that, in S1, the corresponding high-pressure equipment is selected according to the combined pressure, and the high-pressure equipment can be a six-sided top press or a two-stage propulsion press.

[0050] It should be noted that in S1, in order to prevent the azide compound from absorbing water, the operation of placing the azide compound in an inert metal cylinder must be performed in a glove box.

[0051] It should be noted that, in S1, the diameter of the inert metal cylinder is 6 to 30 mm and the thickness is 0.5 mm. The size of the inert metal cylinder is mainly determined by the target sample amount to be prepared.

[0052] It should be noted that in S2, the target pressure range required for the synthesis of cg-PN materials in the high-pressure chamber is 2GPa~10GPa, for example, 2GPa, 3GPa, 4GPa, 5GPa, 6GPa, 7GPa, 8GPa, and 9GPa; the target temperature range is 150℃~550℃, for example, 150℃, 200℃, 300℃, 400℃, 500℃, and 550℃; the holding time is 20min~120min, for example, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, and 110min.

[0053] Specifically, in S2, when the azide compound is NH4N3, the high pressure is 2 GPa to 7 GPa, for example, 2 GPa, 3 GPa, 4 GPa, 5 GPa, 6 GPa, or 7 GPa; the high temperature is 150 to 250° C., for example, 150° C., 180° C., 200° C., or 220° C. Preferably, the high pressure is 3 GPa to 7 GPa, and the high temperature is 150 to 220° C.

[0054] Specifically, in S2, when the azide compound is LiN3, the high pressure is 2 GPa to 7 GPa, for example, 2 GPa, 3 GPa, 4 GPa, 5 GPa, 6 GPa, and 7 GPa; the high temperature is 150 to 290° C., for example, 150° C., 170° C., 190° C., 210° C., 230° C., and 260° C. Preferably, the high pressure is 3 GPa to 7 GPa, and the high temperature is 150 to 260° C.

[0055] Specifically, in S2, when the azide compound is NaN3, the high pressure is 2 GPa to 7 GPa, for example, 2 GPa, 3 GPa, 4 GPa, 5 GPa, 6 GPa, and 7 GPa; the high temperature is 250 to 380° C., for example, 250° C., 280° C., 300° C., 320° C., and 350° C. Preferably, the high pressure is 3 GPa to 7 GPa, and the high temperature is 250 to 350° C.

[0056] Specifically, in S2, when the azide compound is KN3, the high pressure is 2 GPa to 7 GPa, for example, 2 GPa, 3 GPa, 4 GPa, 5 GPa, 6 GPa, and 7 GPa; the high temperature is 250 to 550° C., for example, 300° C., 330° C., 350° C., 370° C., 390° C., 410° C., 430° C., 450° C., 470° C., 510° C., 530° C., and 550° C. Preferably, the high temperature is 300 to 550° C.

[0057] It should be noted that, in S3, the cooling time of the quenching treatment is generally controlled within 1 minute.

[0058] Specifically, in S3, the cooling rate of the quenching treatment is 100-150°C / s, for example, 110°C / s, 120°C / s, or 130°C / s.

[0059] It should be noted that in S3, the pressure relief rate is 0.5 GPa / min to 1 GPa / min, for example, 0.6 GPa / min, 0.7 GPa / min, 0.8 GPa / min, and 0.9 GPa / min.

[0060] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0061] S01. Select the appropriate high-pressure equipment according to the synthetic pressure of the target material;

[0062] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0063] The present invention also provides an atomic polymerized nitrogen material, which is prepared by the above preparation method.

[0064] Specifically, the atomically polymerized nitrogen material (cg-PN) of the present invention is a three-dimensional network of polymerized nitrogen structures, formed by covalent N-N single bonds. This cg-PN material has a unique chemical bonding structure, which gives it a structurally high energy storage capacity.

[0065] Specifically, the atomic polymerized nitrogen material prepared by the method of the present invention reduces the kinetic instability of the polymerized nitrogen material and can maintain its structure and performance under normal pressure, breaking through the limitation of traditional technology that polymerized nitrogen can only exist under extremely high pressure.

[0066] Specifically, the atomically polymerized nitrogen material prepared by the preparation method of the present invention is a very ideal high-energy density material with a wide range of potential applications, especially in high-energy storage and high-efficiency fuel.

[0067] The preparation method of the present invention can produce a high content of cg-PN. For example, in the Raman spectrum, the intensity of the Raman peak corresponding to the A mode of cg-PN is 1 to 7 times that of the characteristic peak of the raw material. This preparation method not only significantly improves the production efficiency of cg-PN, but also ensures that the prepared cg-PN material can maintain its structural stability under normal pressure. The method of the present invention has good operability and industrial application prospects, and is expected to bring new breakthroughs in the preparation of high-energy materials and provide important technical support for the research and development of energy materials.

[0068] The embodiments and comparative examples of the present invention use a ReniShaw Raman spectrometer to perform Raman spectrum measurement, with a laser wavelength of 532 nm, a grating of 2400 l / mm, a power output of 0.5% to 5% (for example, 0.5%, 1% or 5%), an integration time of 10 to 120 s (for example, 10 s, 30 s, 60 or 120 s), an integration number of 1 to 4 times (for example, 1 time, 2 times, 3 times or 4 times), and a Raman spectrum test range of 100 to 1500 cm -1 .

[0069] Example 1

[0070] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0071] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0072] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0073] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0074] Specifically, in S1, the azide compound is KN3.

[0075] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0076] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0077] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0078] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0079] Specifically, in S1, to prevent KN3 from absorbing water, the operation of placing KN3 in an inert metal cylinder is performed in a glove box.

[0080] Specifically, in S1, the inert metal cylinder has a diameter of 6 mm and a thickness of 0.5 mm.

[0081] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0082] Specifically, in S2, the target pressure is 7 GPa.

[0083] Specifically, in S2, the target temperature is 250°C and the holding time is 60 minutes.

[0084] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0085] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0086] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 1 As shown in the Raman spectrum, at 146 cm -1 、634cm -1 、1269cm -1 and 1341cm -1 There are four obvious strong peaks at 146cm -1 、1269cm -1 and 1341cm -1 Corresponding to N3 - , 634cm -1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 8332, which is 1.2 times that of the characteristic peak of the raw material KN3.

[0087] Example 2

[0088] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0089] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0090] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0091] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0092] Specifically, in S1, the azide compound is KN3.

[0093] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0094] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0095] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0096] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0097] Specifically, in S1, to prevent KN3 from absorbing water, the operation of placing KN3 in an inert metal cylinder is performed in a glove box.

[0098] Specifically, in S1, the inert metal cylinder has a diameter of 6 mm and a thickness of 0.5 mm.

[0099] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0100] Specifically, in S2, the target pressure is 7 GPa.

[0101] Specifically, in S2, the target temperature is 400°C and the holding time is 60 minutes.

[0102] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0103] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0104] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 2 As shown in the Raman spectrum, at 145 cm -1 、634cm -1 、1269cm -1 and 1341cm -1 There are four obvious strong peaks at 145cm -1 、1269cm -1 and 1341cm -1 Corresponding to N3 - , 634cm-1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 9900, which is three times that of the characteristic peak of the raw material KN3.

[0105] Example 3

[0106] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0107] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0108] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0109] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0110] Specifically, in S1, the azide compound is KN3.

[0111] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0112] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0113] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0114] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0115] Specifically, in S1, to prevent KN3 from absorbing water, the operation of placing KN3 in an inert metal cylinder is performed in a glove box.

[0116] Specifically, in S1, the inert metal cylinder has a diameter of 6 mm and a thickness of 0.5 mm.

[0117] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0118] Specifically, in S2, the target pressure is 7 GPa.

[0119] Specifically, in S2, the target temperature is 450°C and the holding time is 60 minutes.

[0120] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0121] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0122] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 3 As shown in the Raman spectrum, at 146 cm -1 、634cm -1 、1269cm -1 and 1340cm -1 There are four obvious strong peaks at 146cm -1 、1269cm -1 and 1340cm -1 Corresponding to N3 - , 634cm -1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 15734, which is 6.4 times that of the characteristic peak of the raw material KN3.

[0123] Example 4

[0124] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0125] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0126] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0127] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0128] Specifically, in S1, the azide compound is KN3.

[0129] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0130] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0131] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0132] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0133] Specifically, in S1, to prevent KN3 from absorbing water, the operation of placing KN3 in an inert metal cylinder is performed in a glove box.

[0134] Specifically, in S1, the inert metal cylinder has a diameter of 6 mm and a thickness of 0.5 mm.

[0135] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0136] Specifically, in S2, the target pressure is 7 GPa.

[0137] Specifically, in S2, the target temperature is 550°C and the holding time is 60 minutes.

[0138] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0139] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0140] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 4 As shown in the Raman spectrum, at 143 cm -1 、634cm -1 、1269cm -1 and 1340cm -1 There are four obvious strong peaks at 143cm -1 、1269cm -1 and 1340cm -1 Corresponding to N3 - , 634cm -1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 6935, which is 4 times that of the characteristic peak of the raw material KN3.

[0141] Example 5

[0142] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0143] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0144] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0145] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0146] Specifically, in S1, the azide compound is KN3.

[0147] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0148] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0149] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0150] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0151] Specifically, in S1, to prevent KN3 from absorbing water, the operation of placing KN3 in an inert metal cylinder is performed in a glove box.

[0152] Specifically, in S1, the inert metal cylinder has a diameter of 6 mm and a thickness of 0.5 mm.

[0153] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0154] Specifically, in S2, the target pressure is 2 GPa.

[0155] Specifically, in S2, the target temperature is 450°C and the holding time is 60 minutes.

[0156] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0157] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0158] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 5 As shown in the Raman spectrum, at 143 cm -1 、634cm -1 、1269cm -1 and 1340cm -1 There are four obvious strong peaks at 143cm -1 、1269cm-1 and 1340cm -1 Corresponding to N3 - , 634cm -1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 1393, which is 4.9 times that of the characteristic peak of the raw material KN3.

[0159] Example 6

[0160] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0161] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0162] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0163] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0164] Specifically, in S1, the azide compound is KN3.

[0165] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0166] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0167] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0168] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0169] Specifically, in S1, to prevent KN3 from absorbing water, the operation of placing KN3 in an inert metal cylinder is performed in a glove box.

[0170] Specifically, in S1, the inert metal cylinder has a diameter of 6 mm and a thickness of 0.5 mm.

[0171] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0172] Specifically, in S2, the target pressure is 6 GPa.

[0173] Specifically, in S2, the target temperature is 450°C and the holding time is 30 minutes.

[0174] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0175] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0176] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 6 As shown in the Raman spectrum, at 144 cm -1 、634cm -1 、1269cm -1 and 1340cm -1 There are four obvious strong peaks at 144cm -1 、1269cm -1 and 1340cm -1 Corresponding to N3 - , 634cm -1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 6430, which is 2.6 times that of the characteristic peak of the raw material KN3.

[0177] Example 7

[0178] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0179] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0180] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0181] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0182] Specifically, in S1, the azide compound is NaN3.

[0183] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0184] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0185] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0186] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0187] Specifically, in S1, in order to prevent NaN3 from absorbing water, the operation of placing NaN3 in an inert metal cylinder is performed in a glove box.

[0188] Specifically, in S1, the inert metal cylinder has a diameter of 6 mm and a thickness of 0.5 mm.

[0189] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0190] Specifically, in S2, the target pressure is 6 GPa.

[0191] Specifically, in S2, the target temperature is 350°C and the holding time is 60 minutes.

[0192] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0193] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0194] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 7 As shown in the Raman spectrum, at 145 cm -1 、634cm -1 、1269cm -1 and 1341cm -1 There are four obvious strong peaks at 145cm -1 、1269cm -1 and 1341cm -1 Corresponding to N3 - , 634cm -1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 7687, which is 3.4 times that of the characteristic peak of the raw material NaN3.

[0195] Example 8

[0196] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0197] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0198] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0199] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0200] Specifically, in S1, the azide compound is NaN3.

[0201] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0202] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0203] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0204] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0205] Specifically, in S1, in order to prevent NaN3 from absorbing water, the operation of placing NaN3 in an inert metal cylinder is performed in a glove box.

[0206] Specifically, in S1, the inert metal cylinder has a diameter of 6 mm and a thickness of 0.5 mm.

[0207] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0208] Specifically, in S2, the target pressure is 6 GPa.

[0209] Specifically, in S2, the target temperature is 250°C and the holding time is 120 minutes.

[0210] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0211] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0212] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 8 As shown in the Raman spectrum, at 147 cm -1 、634cm -1 、1269cm -1 and 1341cm -1 There are four obvious strong peaks at 147cm -1、1269cm -1 and 1341cm -1 Corresponding to N3 - , 634cm -1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 12887, which is 2.2 times that of the characteristic peak of the raw material NaN3.

[0213] Example 9

[0214] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0215] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0216] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0217] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0218] Specifically, in S1, the azide compound is LiN3.

[0219] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0220] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0221] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0222] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0223] Specifically, in S1, the inert metal cylinder has a diameter of 3 mm and a thickness of 0.5 mm.

[0224] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0225] Specifically, in S2, the target pressure is 7 GPa.

[0226] Specifically, in S2, the target temperature is 260°C and the holding time is 60 minutes.

[0227] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0228] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0229] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 9 As shown in the Raman spectrum, at 148 cm -1 、634cm -1 、1269cm -1 and 1341cm -1 There are four obvious strong peaks at 148cm -1 、1269cm -1 and 1341cm -1 Corresponding to N3 - , 634cm -1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 1574, which is 1.9 times that of the characteristic peak of the raw material LiN3.

[0230] Example 10

[0231] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0232] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0233] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0234] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0235] Specifically, in S1, the azide compound is LiN3.

[0236] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0237] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0238] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0239] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0240] Specifically, in S1, the inert metal cylinder has a diameter of 3 mm and a thickness of 0.5 mm.

[0241] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0242] Specifically, in S2, the target pressure is 7 GPa.

[0243] Specifically, in S2, the target temperature is 150°C and the holding time is 100 minutes.

[0244] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0245] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0246] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 10 As shown in the Raman spectrum, at 148 cm -1 、634cm -1 、1269cm -1 and 1341cm -1 There are four obvious strong peaks at 148cm -1 、1269cm -1 and 1341cm -1 Corresponding to N3 - , 634cm -1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 4653, which is 3.2 times that of the characteristic peak of the raw material LiN3.

[0247] Example 11

[0248] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0249] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0250] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0251] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0252] Specifically, in S1, the azide compound is NH4N3.

[0253] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0254] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0255] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0256] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0257] Specifically, in S1, the inert metal cylinder has a diameter of 3 mm and a thickness of 0.5 mm.

[0258] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0259] Specifically, in S2, the target pressure is 7 GPa.

[0260] Specifically, in S2, the target temperature is 220°C and the holding time is 30 minutes.

[0261] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0262] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0263] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 11 As shown in the Raman spectrum, at 147 cm -1 、634cm -1 、1267cm -1 and 1341cm -1 There are four obvious strong peaks at 147cm -1 、1267cm -1 and 1341cm -1 Corresponding to N3 - , 634cm -1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 4385, which is 2.3 times that of the characteristic peak of the raw material NH4N3.

[0264] Example 12

[0265] This embodiment provides a method for preparing an atomically polymerized nitrogen material, comprising the following steps:

[0266] S1. Encapsulating the azide compound in an inert metal cylinder and then placing it in a high-pressure chamber;

[0267] S2. Pressurize the raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0268] S3. Perform quenching treatment under high pressure conditions: quickly lower the temperature of the sample location to room temperature, and then release the pressure to obtain atomically polymerized nitrogen material (cg-PN).

[0269] Specifically, in S1, the azide compound is NH4N3.

[0270] Specifically, the material of the inert metal cylinder is gold, which does not react with the raw material and can prevent N3 - It escapes in the form of N2 without participating in the reaction.

[0271] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0272] S01 select the corresponding high-pressure equipment six-sided top press according to the synthetic pressure of the target material;

[0273] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0274] Specifically, in S1, the inert metal cylinder has a diameter of 6 mm and a thickness of 0.5 mm.

[0275] Specifically, in S2, when pressurizing, the six top hammers (upper, lower, left, right, front and rear) synchronously squeeze the cubic sample assembly block under the push of oil pressure, thereby generating high pressure in the sample cavity.

[0276] Specifically, in S2, the target pressure is 6 GPa.

[0277] Specifically, in S2, the target temperature is 150°C and the holding time is 60 minutes.

[0278] Specifically, the quenching treatment in S3 has a cooling rate of 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0279] Specifically, in S3, the pressure relief rate is 0.6 GPa / min.

[0280] The Raman spectrum of the atomically polymerized nitrogen material (cg-PN) prepared in this example is shown in FIG. Figure 12 As shown in the Raman spectrum, at 145 cm -1、634cm -1 、1268cm -1 and 1340cm -1 There are four obvious strong peaks at 145cm -1 、1268cm -1 and 1340cm -1 Corresponding to N3 - , 634cm -1 The Raman peak corresponding to the A mode of cg-PN has an intensity of 6912, which is 4.3 times that of the characteristic peak of the raw material NH4N3.

[0281] Comparative Example 1

[0282] This comparative example provides a method for preparing a polymeric nitrogen material. The overall steps are the same as those in Example 1, except that:

[0283] In step S2, the target temperature is 140°C and the heating time is 30 minutes.

[0284] The Raman spectrum of the synthetic compound of this comparative example is as follows Figure 13 As shown, the Raman spectrum is at 634 cm -1 There is no peak at , so cg-PN is not generated.

[0285] Comparative Example 2

[0286] This comparative example provides a method for preparing a polymerized nitrogen (cg-PN) material. The overall steps are the same as those in Example 1, except that:

[0287] In step S2, the target temperature is 700°C and the heating time is 30 minutes.

[0288] The Raman spectrum of the synthetic compound of this comparative example is as follows Figure 14 As shown, the Raman spectrum is at 634 cm -1 There is no peak at , so cg-PN is not generated.

[0289] Comparative Example 3

[0290] This comparative example provides a method for preparing a polymerized nitrogen (cg-PN) material. The overall steps are the same as those in Example 1, except that:

[0291] In step S2, the target pressure is 1 GPa.

[0292] The Raman spectrum of the synthetic compound of this comparative example is as follows Figure 15 As shown, the Raman spectrum is at 634 cm -1 There is no peak at , so cg-PN is not generated.

[0293] Comparative Example 4

[0294] This comparative example provides a method for preparing a polymerized nitrogen (cg-PN) material. The overall steps are the same as those in Example 7, except that:

[0295] In step S2, the target temperature is 500°C and the heating time is 30 minutes.

[0296] The Raman spectrum of the synthetic compound of this comparative example is as follows Figure 16 As shown, the Raman spectrum in this comparative example is at 634 cm -1 There is no peak at , so cg-PN is not generated.

[0297] Comparative Example 5

[0298] This comparative example provides a method for preparing a polymeric nitrogen (cg-PN) material. The overall steps are the same as those in Example 9, except that:

[0299] In step S2, the target temperature is 450°C and the heating time is 30 minutes.

[0300] The Raman spectrum of the synthetic compound of this comparative example is as follows Figure 17 As shown, the Raman spectrum in this comparative example is at 634 cm -1 There is no peak at , so cg-PN is not generated.

[0301] Comparative Example 6

[0302] This comparative example provides a method for preparing a polymeric nitrogen (cg-PN) material. The overall steps are the same as those in Example 11, except that:

[0303] In step S2, the target temperature is 400°C and the heating time is 30 minutes.

[0304] In this comparative example, no product was obtained due to the high temperature.

[0305] 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. A method for preparing an atomically polymerized nitrogen material, characterized in that: The preparation method obtains the atomic polymerized nitrogen material by directly quenching the azide compound from high temperature to room temperature under high pressure; The pressure range of the high pressure is 2GPa to 10GPa; The high temperature range is 150°C to 550°C; The azide compound includes one or more of KN3, NaN3, LiN3 and NH4N3; When the azide compound is NH4N3, the high temperature is 150-250°C; When the azide compound is LiN3, the high temperature is 150-260°C; When the azide compound is NaN3, the high temperature is 250-350°C; When the azide compound is KN3, the high temperature is 250-550°C.

2. The preparation method according to claim 1, characterized in that The high pressure ranges from 2 GPa to 7 GPa.

3. The preparation method according to claim 1, characterized in that When the azide compound is NH4N3, the high temperature is 150-220°C.

4. The preparation method according to any one of claims 1 to 3, characterized in that The preparation method further comprises: quenching to room temperature and then releasing pressure to obtain the atomic polymerized nitrogen material.

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