Nitrogen and phosphorus co-doped carbon material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of material preparation, in particular to a nitrogen-phosphorus co-doped carbon material and a preparation method and application thereof. The preparation method comprises the following steps: mixing a carbon precursor and water, and performing hydrothermal reaction to obtain brown powder solid; after ball-milling and mixing the brown powder solid, a nitrogen source and a phosphorus source, roasting in inert gas to obtain a nitrogen-phosphorus co-doped carbon material; the nitrogen and phosphorus co-doped carbon material prepared by the method is used for preparing a catalyst loaded with noble metal Pd (OH) 2 / C, shows excellent catalytic activity in two-step hydrogenolysis debenzylation reaction of hexabenzyl hexaazaisowurtzitane (HBIW) and tetraacetyl dibenzyl hexaazaisowurtzitane (TADB), and greatly reduces the synthesis cost of CL-20.

Description

Technical Field

[0001] The present invention relates to the technical field of material preparation, and in particular to a nitrogen-phosphorus co-doped carbon material and a preparation method and application thereof. Background Art

[0002] Carbon materials are a type of material with carbon as the main constituent element. They have broad development prospects and are components of most materials. They have many advantages: good stability, easy structure control, simple and easy to obtain, environmentally friendly and renewable, good electrical conductivity, and unique orderly spatial arrangement of carbon atoms in micro-regions. They are often used as carriers for precious metal loading. After further modification, carbon materials will present unique chemical and physical properties, showing characteristics that are difficult to replace by other materials, and are widely used in various fields. The surface of carbon materials is modified, different functional groups or chemical groups are introduced, the surface structure and chemical properties of carbon materials are regulated, the number distribution of surface chemical functional groups (-COOH, -COO-, -OH, -CO, etc.) and the interaction between active components and carbon carriers are affected, and the loading and adsorption capabilities of carbon materials are improved, so that carbon materials have special properties and uses.

[0003] Hexanitrohexaazaisowurtzitane (HNIW, commonly known as CL-20) is the energetic compound with the highest energy level known so far and is the single explosive with the best comprehensive performance for industrial production.

[0004]

[0005] In the CL-20 synthesis route shown above, a large amount of catalyst is required in the debenzylation process of hexabenzylhexaazaisowurtzitane (HBIW), and the cage-shaped matrix of HBIW is very unstable, which places higher requirements on the activity and stability of the catalyst. At the same time, in the hydrogenolysis debenzylation reaction of tetraacetyldibenzylhexaazaisowurtzitane (TADB), a larger amount of catalyst is required. The two-step hydrogenolysis debenzylation makes the synthesis cost of CL-20 high.

[0006] In the two-step hydrogenolysis benzylation reaction, the solvent system and the acidity and alkalinity of the catalyst surface play an important role in the reaction. Therefore, how to reduce the particle size of the precious metal particles and improve their dispersion on the surface of the carbon carrier to provide more reactive sites and reduce the synthesis cost of CL-20 has become a technical problem that needs to be solved urgently by those skilled in the art. Summary of the invention

[0007] The purpose of the present invention is to provide a nitrogen-phosphorus co-doped carbon material and a preparation method and application thereof, so as to solve the problems existing in the prior art.

[0008] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0009] The present invention provides a method for preparing a nitrogen-phosphorus co-doped carbon material, comprising the following steps:

[0010] 1) mixing a carbon precursor and water and performing a hydrothermal reaction to obtain a brown powder solid;

[0011] 2) The brown powder solid, nitrogen source and phosphorus source are ball-milled and mixed, and then calcined in an inert gas to obtain a nitrogen-phosphorus co-doped carbon material.

[0012] Optionally, the ball milling is performed by adding ball milling beads to a mixture of brown powder solid, nitrogen source and phosphorus source for ball milling;

[0013] The mass ratio of the ball milling beads to the mixture is 10:1 to 50:1;

[0014] The rotation speed of the ball mill is 250 r / min to 400 r / min; and the time of the ball mill is 10 min to 60 min.

[0015] Optionally, the concentration of the carbon precursor in water is 0.1 mol / L to 4.0 mol / L.

[0016] Optionally, the temperature of the hydrothermal reaction is 170° C. to 200° C., and the time is 20 h to 24 h.

[0017] Optionally, the mass ratio of the carbon precursor to the nitrogen source is 15:1 to 1:3; the mass ratio of the carbon precursor to the phosphorus source is 15:1 to 1:3.

[0018] Optionally, the carbon precursor comprises one or more of glucose, fructose, sucrose, starch, lignin, chitosan, sodium gluconate and cellulose.

[0019] Optionally, the nitrogen source is a nitrogen-containing compound, and the nitrogen-containing compound includes one or more of urea, dicyandiamide, melamine, hexamethylenetetramine, lysine, and ammonium salts;

[0020] The phosphorus source is a phosphorus-containing compound, and the phosphorus-containing compound includes one or more of phytate, phosphate, triphenylphosphine and ammonium hydrogen phosphate.

[0021] Optionally, the calcination temperature rise rate is 1°C / min to 10°C / min, the temperature is 600°C to 1400°C, and the time is 1h to 5h; the inert gas comprises one or more of nitrogen, helium and argon.

[0022] The present invention also provides a nitrogen-phosphorus co-doped carbon material prepared by the method for preparing the nitrogen-phosphorus co-doped carbon material.

[0023] The present invention also provides the use of the nitrogen and phosphorus co-doped carbon material in the preparation of a hydrogenolysis debenzylation noble metal-based catalyst.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] In the technical solution of the present invention, the carbon precursor undergoes surface dehydration, polymerization, and carbonization during hydrothermal treatment in the absence of a template, and the original morphology will not be destroyed during mechanical ball milling for heteroatom doping; at the same time, the mechanochemical method can apply mechanical force to various mixtures, and their surface area and contact area are increased to a certain extent. Mechanical energy can be generated and transferred through a solid-state ball mill, and solid ball milling beads with high kinetic energy collide with the wall of the chamber and other solid ball milling beads to crush, bond, break, and re-bond the internal mixture particles, thereby reducing the particle size and increasing the strain in the sample, so that the carbonization product is fully mixed with the nitrogen source and phosphorus source, and the nitrogen and phosphorus can better enter the carbon skeleton during roasting to form defects.

[0026] In the technical solution of the present invention, the doping effect of heteroatoms is optimized by adjusting the ball milling process parameters, selecting the appropriate ball milling speed, time and appropriate ball-to-powder ratio, and improving the preparation efficiency of carbon materials.

[0027] The nitrogen and phosphorus co-doped carbon material prepared by the present invention can effectively increase the type and quantity of the acidity and alkalinity of the carbon material surface, change the charge density distribution and bond length of the carbon atoms near the dopant, increase the defect sites of the carbon material, lead to structural distortion, reduce the particle size of the noble metal particles, and improve the dispersion of the noble metal particles on the surface of the carbon carrier to provide more reactive sites. The hydrogenolysis debenzylation noble metal-based catalyst prepared by using the carbon material of the present invention as a carrier has high activity, and the synthesis cost of CL-20 is reduced.

[0028] The nitrogen and phosphorus co-doped carbon material prepared by the invention has a high surface area and an obvious porous structure; the preparation method provided has simple and mild conditions, a simple process, and readily available and inexpensive raw materials, is suitable for large-scale industrial production, and has broad application prospects.

[0029] The nitrogen and phosphorus co-doped carbon material prepared by the present invention is used for the preparation of a loaded noble metal catalyst. When used for the synthesis of CL-20, the carbon material shows high catalytic activity in the two-step hydrogenolysis debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) and tetraacetyldibenzylhexaazaisowurtzitane (TADB), thereby greatly reducing the synthesis cost of CL-20. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The scanning electron microscope (SEM) images of the carbon materials prepared in Examples 1-4, (a) is 1# carbon material, (b) is 2# carbon material, (c) is 3# carbon material, and (d) is 4# carbon material;

[0031] Figure 2This is a transmission electron microscopy (STEM) image of a Pd(OH)2 / C catalyst prepared using the carbon material prepared in Example 1 as a carrier;

[0032] Figure 3 This is a transmission electron microscopy (STEM) image of a Pd(OH)2 / C catalyst prepared using the carbon material prepared in Example 2 as a carrier;

[0033] Figure 4 The powder Raman spectra of the carbon materials prepared in Example 1-2, (a) is 1# carbon material, (b) is 2# carbon material;

[0034] Figure 5 The 1# carbon material and the 2# carbon material prepared in Example 1-2 are respectively the hydrogen absorption curves of the Pd(OH)2 / C catalyst prepared as the carrier in the TADB hydrogenolysis benzyl reaction. DETAILED DESCRIPTION

[0035] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0036] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0037] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0038] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present application description and examples are exemplary only.

[0039] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0040] The "room temperature" and "normal temperature" mentioned in the present invention are all calculated as 25±2°C unless otherwise specified.

[0041] The raw materials used in the following examples of the present invention are all commercially available.

[0042] The present invention provides a method for preparing a nitrogen-phosphorus co-doped carbon material, comprising the following steps:

[0043] 1) mixing a carbon precursor and water and performing a hydrothermal reaction to obtain a brown powder solid;

[0044] 2) The brown powder solid, nitrogen source and phosphorus source are ball-milled and mixed, and then calcined in an inert gas to obtain a nitrogen-phosphorus co-doped carbon material.

[0045] In the present invention, the ball milling is performed by adding ball milling beads to a mixture of brown powder solid, nitrogen source and phosphorus source for ball milling;

[0046] The mass ratio of the ball mill beads to the mixture is 10:1 to 50:1, preferably 15:1 to 45:1, more preferably 20:1 to 40:1, and even more preferably 25:1 to 30:1;

[0047] The rotation speed of the ball mill is 250 r / min to 400 r / min, preferably 280 r / min to 380 r / min, and more preferably 300 r / min to 350 r / min; the time of the ball mill is 10 min to 60 min, preferably 20 min to 50 min, and more preferably 30 min to 40 min.

[0048] In the present invention, low speed, short time and low ball-to-powder ratio during ball milling will lead to uneven doping of nitrogen and phosphorus sources, while high speed and long time ball milling will lead to local high temperature in the ball milling jar, resulting in the loss of some low melting point volatile samples, and also cause the particle size of the carbon material to change after roasting, affecting its specific surface area and pore structure distribution. The present invention achieves the best effect of heteroatom doping by adjusting ball milling process parameters, selecting appropriate ball milling speed, time and appropriate ball-to-powder ratio, and improving the preparation efficiency of carbon materials.

[0049] In the present invention, the concentration of the carbon precursor in water is 0.1 mol / L to 4.0 mol / L, preferably 0.2 mol / L to 3.0 mol / L, more preferably 0.5 mol / L to 2.5 mol / L, and even more preferably 1.2 mol / L to 2 mol / L.

[0050] In the present invention, the temperature of the hydrothermal reaction is 170°C to 200°C, preferably 175°C to 190°C, more preferably 180°C to 185°C, and the time is 20h to 24h, preferably 21h to 23h, more preferably 22h to 22.5h.

[0051] In the present invention, the mass ratio of the carbon precursor to the nitrogen source is 15:1 to 1:3, preferably 10:1 to 3:1, and more preferably 5:1 to 1:1; the mass ratio of the carbon precursor to the phosphorus source is 15:1 to 1:3, preferably 10:1 to 3:1, and more preferably 5:1 to 1:1.

[0052] In the present invention, the carbon precursor comprises one or more of glucose, fructose, sucrose, starch, lignin, chitosan, sodium gluconate and cellulose, preferably one or more of glucose, fructose and sucrose, and more preferably glucose.

[0053] In the present invention, the nitrogen source is a nitrogen-containing compound, and the nitrogen-containing compound includes one or more of urea, dicyandiamide, melamine, hexamethylenetetramine, lysine, and ammonium salts, preferably one or more of urea, dicyandiamide, lysine, and melamine, and more preferably urea;

[0054] The phosphorus source is a phosphorus-containing compound, which includes one or more of phytate, phosphate, triphenylphosphine and ammonium hydrogen phosphate, preferably one or more of phytate, phosphate and ammonium hydrogen phosphate, and more preferably phytate.

[0055] In the present invention, the calcination heating rate is 1°C / min to 10°C / min, preferably 5°C / min to 10°C / min, further preferably 7°C / min to 10°C / min, and further preferably 9°C / min to 10°C / min. The temperature is 600°C to 1400°C, preferably 500°C to 1200°C, further preferably 700°C to 1000°C, and further preferably 800°C to 900°C. The time is 1h to 5h, preferably 2h to 4h, and further preferably 2.5h to 3h. The inert gas comprises one or more of nitrogen, helium and argon, preferably one or more of nitrogen and helium, and further preferably nitrogen.

[0056] In the present invention, the product obtained by calcination needs to be placed in a hydrochloric acid solution, stirred and dissolved to remove impurities, filtered, washed and dried to obtain a nitrogen-phosphorus co-doped carbon material;

[0057] The mass concentration of the hydrochloric acid solution is 10% to 50%, preferably 10% to 40%, more preferably 15% to 37%, and even more preferably 20% to 30%;

[0058] The stirring time is 4h to 10h, preferably 5h to 8h, and more preferably 6h to 7h;

[0059] The drying temperature is 60°C to 120°C, more preferably 70°C to 100°C, and further preferably 80°C to 90°C.

[0060] The present invention also provides a nitrogen-phosphorus co-doped carbon material prepared by the method for preparing the nitrogen-phosphorus co-doped carbon material.

[0061] The present invention also provides the use of the nitrogen and phosphorus co-doped carbon material in the preparation of a hydrogenolysis debenzylation noble metal-based catalyst.

[0062] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0063] Example 1

[0064] Weigh 3.6 g of glucose and dissolve it in 100 mL of deionized water. Under magnetic stirring, after the glucose is completely dissolved, transfer the uniform solution to a polytetrafluoroethylene liner, and place the liner in a stainless steel autoclave and hydroheat it at 170°C for 24 hours. Filter to obtain a brown solid, and dry it at 80°C for 12 hours. Weigh a certain mass of brown solid, add urea according to the mass ratio of carbon precursor to nitrogen source of 12:1, add phytate according to the mass ratio of carbon precursor to phosphorus source of 6:1, add ball milling beads to the solid mixture at a ratio of 30:1, and ball milling at 300 r / min for 40 minutes. Place the brown solid obtained by mechanical ball milling in a tubular furnace, heat it to 700°C at a rate of 9°C / min in a nitrogen atmosphere, and calcine it for 2 hours. After cooling to room temperature, mix and stir it with 20wt% hydrochloric acid for 6 hours to remove impurity ions, wash it with deionized water, and dry it to obtain 1# carbon material.

[0065] Figure 1 (a) is the SEM image of carbon material 1#. It can be seen from the figure that the material after ball milling and calcination basically retains its original morphology without any change;

[0066] Figure 2 This is a STEM image of the Pd(OH)2 / C catalyst prepared using the carbon material #1 as a carrier. It can be seen from the image that N and P are evenly distributed on the surface of the sphere, and there is no agglomeration of metal particles;

[0067] Figure 4 (a) is the powder Raman spectrum of carbon material 1#. It can be seen from the figure that after the carbon material is doped with nitrogen and phosphorus, there are more surface defects in its carbon skeleton, which leads to an increase in the disorder of the carbon matrix.

[0068] Example 2

[0069] Weigh 7.2 g of glucose and dissolve it in 100 mL of deionized water. Under magnetic stirring, after the glucose is completely dissolved, transfer the uniform solution to a polytetrafluoroethylene liner, and place the liner in a stainless steel autoclave and hydroheat it at 170°C for 24 hours. Filter to obtain a brown solid, and dry it at 80°C for 12 hours. Weigh a certain mass of brown solid, add urea according to the mass ratio of carbon precursor to nitrogen source of 12:1, add phytate according to the mass ratio of carbon precursor to phosphorus source of 3:1, and add ball milling beads to the solid mixture at a ratio of 30:1. Ball milling is performed at 310 r / min for 40 minutes. The brown solid obtained by mechanical ball milling is placed in a tubular furnace, and the temperature is increased to 700°C at a rate of 10°C / min in a helium atmosphere, and then calcined for 2 hours. After cooling to room temperature, it is mixed and stirred with 20wt% hydrochloric acid for 6 hours to remove impurity ions, washed with deionized water, and dried to obtain 2# carbon material.

[0070] Figure 1 (b) is the SEM image of the 1# carbon material. It can be seen from the figure that the material with the doping ratio changed and then ball-milled and calcined basically retains the original morphology without changing;

[0071] Figure 3 This is a transmission STEM image of the Pd(OH)2 / C catalyst prepared using the carbon material of Example 2# as a carrier. It can be seen from the image that N and P are evenly distributed on the surface of the sphere, and there is no agglomeration of metal particles;

[0072] Figure 4 (b) is the powder Raman spectrum of carbon material #1. It can be seen from the figure that after the carbon material is doped with nitrogen and phosphorus, there are more surface defects in its carbon skeleton, which leads to an increase in the disorder of the carbon matrix.

[0073] Example 3

[0074] Weigh 14.4 g of glucose and dissolve it in 100 mL of deionized water. Under magnetic stirring, after the glucose is completely dissolved, transfer the uniform solution to a polytetrafluoroethylene liner, and put the liner into a stainless steel autoclave and hydroheat it at 180°C for 24 hours. Filter to obtain a brown solid, and dry it at 80°C for 12 hours. Weigh a certain mass of brown solid, add urea according to the mass ratio of carbon precursor to nitrogen source of 7:1, add phytate according to the mass ratio of carbon precursor to phosphorus source of 6:1, add ball milling beads: solid mixture at a ratio of 30:1, and ball mill at 300 r / min for 40 minutes. Place the brown solid obtained by mechanical ball milling in a tubular furnace, heat it to 800°C at a rate of 10°C / min in a nitrogen atmosphere, and calcine it for 2 hours. After cooling to room temperature, stir it with 20wt% hydrochloric acid for 7 hours to remove impurity ions, wash it with deionized water, and dry it to obtain 3# carbon material.

[0075] Figure 1(c) is the SEM image of 1# carbon material. It can be seen from the figure that the material with changed doping ratio, ball milled and then calcined basically retains its original morphology without any change.

[0076] Example 4

[0077] Weigh 21.6 g of glucose and dissolve it in 100 mL of deionized water. Under magnetic stirring, after the glucose is completely dissolved, transfer the uniform solution to a polytetrafluoroethylene liner, and place the liner in a stainless steel autoclave and hydroheat it at 180°C for 24 hours. Filter to obtain a brown solid, and dry it at 80°C for 12 hours. Weigh a certain mass of brown solid, add urea according to a mass ratio of 7:1 between the carbon precursor and the nitrogen source, add phytate according to a mass ratio of 3:1 between the carbon precursor and the phosphorus source, add ball milling beads at a ratio of 30:1 between the ball milling beads and the solid mixture, and ball mill at 310 r / min for 40 minutes. Place the brown solid obtained by mechanical ball milling in a tubular furnace, heat it to 800°C at a rate of 10°C / min in a nitrogen atmosphere, and calcine it for 2 hours. After cooling to room temperature, stir it with 20wt% hydrochloric acid for 6 hours to remove impurity ions, wash it with deionized water, and dry it to obtain 4# carbon material.

[0078] Figure 1 (d) is the SEM image of 1# carbon material. It can be seen from the figure that the material with changed doping ratio, ball milled and then calcined basically retains its original morphology without any change.

[0079] Comparative Example 1

[0080] The only difference from Example 1 is that no nitrogen source or phosphorus source is added for mechanical ball milling, and the carbon carrier C* is obtained after calcination.

[0081] The specific surface area and pore size analysis of the carbon materials of Comparative Example C*, Example 1-1#, and Example 2-2# are shown in Table 1 below:

[0082] Table 1 BET specific surface area data of carbon materials prepared in Comparative Example 1 and Examples 1-2

[0083]

[0084] It can be seen from Table 1 that appropriate ball milling speed, time, and ball-to-powder ratio can effectively improve the doping of nitrogen and phosphorus atoms and introduce an appropriate amount of defect sites.

[0085] Application example: The nitrogen and phosphorus co-doped carbon materials 1-1# and 2-2# samples obtained in Examples 1 and 2 were used as carriers, and the corresponding Pd(OH)2 / C catalysts (Pd(OH)2 / C-1-1#, Pd(OH)2 / C-2-2#) were prepared by the deposition precipitation method. The catalytic activity was evaluated using the hydrogenolysis debenzylation reaction of HBIW and TADB as a probe. The reaction conditions were as follows: HBIW 25g, catalyst 0.5g, DMF 50ml, A2CO 25ml, PhBr 0.5ml; TADB 20g, catalyst 0.66g, CH3COOH 80ml, H2O 20ml, perchloric acid 0.5ml. The hydrogen was replaced three times, and the reaction was stirred at 43°C for 12h. The hydrogen absorption curves of the two catalyst samples in the hydrogenolysis debenzylation reaction of TADB are shown in the attached figure. Figure 5 The activities of Pd(OH)2 / C*, Pd(OH)2 / C-1-1#, and Pd(OH)2 / C-2-2# in the hydrogenolysis reactions of HBIW and TADB are shown in Table 2.

[0086] Table 2 Activity of Pd(OH)2 / C*, Pd(OH)2 / C-1-1#, and Pd(OH)2 / C-2-2# in the hydrogenolysis of HBIW and TADB

[0087]

[0088] Pd(OH)2 / C* represents a catalyst prepared using the carbon material prepared in Comparative Example 1 as a carrier.

[0089] Depend on Figure 5 It can be seen that the preparation of catalysts using nitrogen and phosphorus doped materials loaded with precious metals can effectively increase the hydrogen evolution rate during the TADB hydrogenolysis debenzylation reaction.

[0090] It can be seen from Table 2 that the catalyst prepared by loading precious metals on nitrogen and phosphorus-doped carbon materials can effectively improve the conversion rate of TADB.

[0091] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a nitrogen-phosphorus co-doped carbon material, characterized in that: The following steps are involved: 1) mixing a carbon precursor and water and performing a hydrothermal reaction to obtain a brown powder solid; 2) The brown powder solid, nitrogen source and phosphorus source are ball-milled and mixed, and then calcined in an inert gas to obtain a nitrogen-phosphorus co-doped carbon material.

2. The method for preparing nitrogen and phosphorus co-doped carbon material according to claim 1, characterized in that: The ball milling is performed by adding ball milling beads to a mixture of brown powder solid, nitrogen source and phosphorus source for ball milling; The mass ratio of the ball milling beads to the mixture is 10:1 to 50:1; The rotation speed of the ball mill is 250 r / min to 400 r / min; and the time of the ball mill is 10 min to 60 min.

3. The method for preparing nitrogen and phosphorus co-doped carbon material according to claim 1, characterized in that: The concentration of the carbon precursor in water is 0.1 mol / L to 4.0 mol / L.

4. The method for preparing nitrogen and phosphorus co-doped carbon material according to claim 1, characterized in that: The temperature of the hydrothermal reaction is 170° C. to 200° C., and the time is 20 h to 24 h.

5. The method for preparing the nitrogen-phosphorus co-doped carbon material according to claim 1 or 3, characterized in that: The mass ratio of the carbon precursor to the nitrogen source is 15:1 to 1:3; the mass ratio of the carbon precursor to the phosphorus source is 15:1 to 1:

3.

6. The method for preparing nitrogen and phosphorus co-doped carbon material according to claim 5, characterized in that: The carbon precursor comprises one or more of glucose, fructose, sucrose, starch, lignin, chitosan, sodium gluconate and cellulose.

7. The method for preparing nitrogen and phosphorus co-doped carbon material according to claim 1, characterized in that: The nitrogen source is a nitrogen-containing compound, and the nitrogen-containing compound includes one or more of urea, dicyandiamide, melamine, hexamethylenetetramine, lysine, and ammonium salt; The phosphorus source is a phosphorus-containing compound, and the phosphorus-containing compound includes one or more of phytate, phosphate, triphenylphosphine and ammonium hydrogen phosphate.

8. The method for preparing nitrogen and phosphorus co-doped carbon material according to claim 1, characterized in that: The calcination temperature rise rate is 1°C / min to 10°C / min, the temperature is 600°C to 1400°C, and the time is 1h to 5h; the inert gas includes one or more of nitrogen, helium and argon.

9. The nitrogen and phosphorus co-doped carbon material prepared by the method for preparing the nitrogen and phosphorus co-doped carbon material according to any one of claims 1 to 8.

10. Use of the nitrogen and phosphorus co-doped carbon material according to claim 9 in the preparation of a noble metal-based catalyst for hydrogenolysis debenzylation.

Images