CN116986584B - Preparation method of nitrogen, phosphorus and iron doped carbon materials and their application in rubber - Google Patents

Abstract

The invention relates to a preparation method of a carbon material doped with nitrogen, phosphorus and iron and application of the carbon material in rubber, comprising the following steps of: A. the mass ratio is 3-7: 1-4: 1.5-5.3: 1.3 to 4.1: 2.1-6.4 of chitosan, diammonium hydrogen phosphate, (ethane-1, 2-diyl bis (phosphino)) tetramethanol, zinc chloride and potassium ferrate, and standing to obtain an intermediate product; B. and (3) under the air atmosphere, treating the intermediate product at 180-220 ℃ for 2-4 hours, then placing the intermediate product in an inert atmosphere for carbonization reaction, and cooling to room temperature to obtain the nitrogen, phosphorus and iron doped carbon material. The carbon material prepared by the method can effectively reinforce rubber.

Description

Preparation method of nitrogen, phosphorus and iron doped carbon materials and their application in rubber

Technical field

The invention relates to a preparation method of carbon materials doped with nitrogen, phosphorus and iron and their application in rubber, and belongs to the technical field of carbon materials.

Background technique

Carbon is one of the most common elements distributed in nature. In addition to forming single bonds through sp ³ hybridization, carbon can also form stable double bonds and triple bonds through sp ³ and sp hybridization between its atoms. Therefore, it can form very different structures and properties. Allotropes, such as zero-dimensional carbon black and fullerene, one-dimensional carbon nanotubes and carbon nanofibers, two-dimensional graphene, etc. From traditional carbon black to the latest two-dimensional graphene, carbon materials have been widely used in adsorbents, catalysts, fuel cells, electrode materials for secondary batteries, and supercapacitors with their unique and excellent mechanical, electrical and thermal properties. , composite materials, gas sensors, solar cells and various electronic devices and other fields.

Carbon materials can be added to rubber as fillers, which can enhance the physical, thermal, electrical, gas/liquid barrier and other properties of rubber, and can reduce the production cost of rubber products. At present, the carbon materials commonly used in rubber are graphite, carbon black, graphene, graphene oxide, carbon fiber, and carbon nanotubes. However, these carbon materials also have many defects and cannot fully exert their due reinforcing effects. For example, in rubber Agglomeration easily occurs in the matrix and it is difficult to combine well with the rubber matrix. Rubber waterstops are used as anti-seepage materials in concrete joints between buildings and water and soil structures. The strength of the rubber, including hardness, tensile strength, and tearing degree, will affect the overall seismic resistance and service life of the bridge structure.

Therefore, it is very necessary to develop carbon materials with good reinforcing effect.

Contents of the invention

The purpose of the present invention is to overcome the defects existing in the prior art, provide a nitrogen-, phosphorus-, and iron-doped carbon material that can effectively reinforce the mechanical properties of rubber, and provide its preparation method and its application in rubber.

In order to solve the above problems, the technical solutions adopted by the present invention are:

Technical theme one

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

A. Combine chitosan, diammonium hydrogen phosphate, (ethane-1,2-diylbis(phosphine)) with a mass ratio of 3~7:1~4:1.5~5.3:1.3~4.1:2.1~6.4 Ball mill tetramethanol, zinc chloride and potassium ferrate and let stand to obtain an intermediate product;

B. In an air atmosphere, treat the intermediate product at 180-220°C for 2-4 hours, then place it in an inert atmosphere for carbonization reaction, and cool to room temperature to obtain nitrogen, phosphorus, and iron-doped carbon materials.

As a preferred embodiment of the present invention, the mass of chitosan, diammonium hydrogen phosphate, (ethane-1,2-diylbis(phosphino))tetramethanol, zinc chloride and potassium ferrate in step A The ratio is 5:2:2:2:3.

As a preferred embodiment of the present invention, the ball milling step of step A is specifically ball milling for 15-25 minutes, pause for 4-6 minutes, and repeated 2-4 times.

As a preferred embodiment of the present invention, the rotation speed of the ball mill in step A is 450-550 rpm.

As a preferred embodiment of the present invention, the step of letting stand is specifically for 50-70 minutes.

As a preferred embodiment of the present invention, in step B, the temperature of the carbonization reaction is 850-950°C and the time is 2.5-3.5 hours.

As a preferred embodiment of the present invention, the carbonization step of Step B is to continuously introduce protective gas at a rate of 15~25mL/min, first increase the temperature from room temperature to 300±10°C at a rate of 1.2~1.7°C/min, and then Raise the temperature to 900±10℃ at a rate of 1.8~2.2℃/min and then maintain it for 2.5~3.5 hours.

As a preferred embodiment of the present invention, the viscosity of the chitosan is 200-400 mPa.s.

Technical topic two

Application of a nitrogen-, phosphorus-, and iron-doped carbon material obtained by the preparation method provided in Technical Topic 1 in the field of rubber.

In some embodiments of the invention, the application is the preparation of rubber waterstops.

In some embodiments of the present invention, the raw materials of the rubber waterstop include butyl rubber, nitrogen, phosphorus, iron-doped carbon materials, ZnO, hard Fatty acid, accelerator and sulfur; the accelerator is dibenzothiazole disulfide (DM) and N-cyclohexyl-2-benzothiazole hypoxanamide (CZ) with a mass ratio of 1:0.5:0.2:2:0.2 ), thiuram disulfide (TMTD), dithiodimorpholine (DTDM) and 2-thiol benzothiazole (M).

Preparation process of rubber waterstop: Put 100kg of butyl rubber into the internal mixer to break the rubber, plasticize for 30 seconds, and lift the bolt; add 40kg of nitrogen, phosphorus, and iron-doped carbon materials into the internal mixer for one stage of mixing. Knead for 2 minutes, then add 5kg ZnO and 1kg stearic acid together. The mixing time is maintained for about 6 minutes, the temperature is about 140°C, and the glue is discharged after 90 s; then adjust the roller distance of the open mill, pour the glue 3 times and then remove the tablets. and cool to room temperature;

Then mix 2kg of sulfur and 1kg of accelerator on the open mill for two-stage mixing, thinning, triangular wrapping and rolling three times each, and remove the pieces; put the mixed rubber into the mold and vulcanize to form the rubber. The vulcanization The temperature is 145°C, the vulcanization time is 180s, and the vulcanization pressure is 10MPa; the accelerator is dibenzothiazole disulfide (DM) and N-cyclohexyl-2-benzo with a mass ratio of 1:0.5:0.2:2:0.2. Thiazole hypoxanthamide (CZ), thiuram disulfide (TMTD), dithiodimorpholine (DTDM), 2-thiol benzothiazole (M).

The beneficial effects produced by adopting the above technical solutions are:

In the carbon material preparation method provided by the present invention, each component is coordinated and doped with metal elements at the same time, which improves the dispersion of the carbon material. After being applied to rubber, it can fully contact the rubber, effectively avoid agglomeration, and thereby effectively reinforce rubber. The rubber waterstop was prepared using the carbon material prepared by the method of the present invention. After testing, it complies with the Q/CR 562.2-2017 "Railway Tunnel Anti-Drainage Materials Part 2: Waterstop" standard.

In the present invention, potassium ferrate functions as an oxidant and pore-forming agent. It can directly oxidize amino groups into nitric acid groups at high temperatures, prevent the release of nitrogen atoms, have nitrogen fixation effects, and increase the nitrogen content of the product; potassium ferrate decomposes at high temperatures to produce oxygen. It has an etching effect on materials, can regulate product morphology, increase porosity, and increase specific surface area; potassium ferrate is also a good iron source and can interact with (ethane-1,2-diyl bis(phosphine)) Tetracarbinol coordinates and plays the role of doping iron and phosphorus.

Diammonium hydrogen phosphate decomposes under air atmosphere and high temperature to release ammonia gas and water. Ammonia gas and water are excellent pore-forming agents that can increase the specific surface area of the material. Amino groups and phosphate groups can generate hydrogen bonds with raw materials and promote Raw material polymerization. In addition, diammonium hydrogen phosphate is also a source of nitrogen and phosphorus.

(Ethane-1,2-diylbis(phosphine))tetramethanol is a phosphine ligand, which can coordinate with metals and play a role in locking metals. It is also a phosphorus source; The hydroxyl group of bis(phosphino)tetramethanol can form bonds with the hydroxyl group and amino group of chitosan to increase the product yield.

Description of drawings

Figure 1 is a particle size distribution diagram of the carbon material prepared in Example 1 of the present invention.

Detailed ways

In order to make the purpose, technical solutions and advantages of the present invention clearer, the invention is described clearly and completely below with reference to specific embodiments.

Each substance used in this example can be purchased commercially. Chitosan was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS number: 9012-76-4, and viscosity is 200-400mPa.s.

Example 1

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

A. Take 5 grams of chitosan, 2 grams of diammonium hydrogen phosphate, 2 grams of (ethane-1,2-diylbis(phosphine))tetramethanol, 2 grams of zinc chloride and 3 grams of potassium ferrate and put it in Mill the ball three times in the ball milling tank of the high-energy ball mill. Each time, the ball mill rotates at 500 rpm for 20 minutes and pauses for 5 minutes. Finally, the intermediate product is obtained after standing for 1 hour;

B. Place the intermediate product in a carbonization furnace, treat it at 200°C for 3 hours in an air atmosphere, and then perform a carbonization reaction in a nitrogen atmosphere. During the carbonization reaction, nitrogen gas is continuously introduced at a rate of 20 mL/min. Start with The room temperature is raised to 300°C at a rate of 1.5°C/min, then raised to 900°C at a rate of 2.0°C/min, kept for 3 hours, and then lowered to room temperature to obtain black nitrogen, phosphorus, and iron-doped carbon materials. .

The parameters of the prepared carbon material are as follows: specific surface area 745 m ² /g, particle size distribution 20-38nm.

The particle size distribution of the prepared carbon material was analyzed, as shown in Figure 1.

Example 2

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

A. Take 3 grams of chitosan, 4 grams of diammonium hydrogen phosphate, 1.5 grams of (ethane-1,2-diyl bis(phosphine)) tetramethanol, 4.1 grams of zinc chloride and 2.1 grams of potassium ferrate and put them in The ball is milled twice in the ball grinding tank of the high-energy ball mill. Each time, the ball mill is rotated at 550 rpm for 15 minutes and paused for 6 minutes. Finally, the intermediate product is obtained after standing for 50 minutes;

B. Place the intermediate product in a carbonization furnace, treat it at 220°C for 4 hours in an air atmosphere, and then perform a carbonization reaction in a nitrogen atmosphere. During the carbonization reaction, nitrogen is continuously introduced at a rate of 15 mL/min. First, start at room temperature. Raise the temperature to 300°C at a rate of 1.7°C/min, then increase the temperature to 950°C at a rate of 1.8°C/min, keep it for 2.5 hours, and then lower it to room temperature to obtain a black nitrogen-, phosphorus-, and iron-doped carbon material.

The parameters of the prepared carbon material are as follows: specific surface area 737 m ² /g, particle size distribution 15-40nm.

Example 3

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

A. Take 7 grams of chitosan, 1 gram of diammonium hydrogen phosphate, 5.3 grams of (ethane-1,2-diyl bis(phosphine)) tetramethanol, 1.3 grams of zinc chloride and 6.4 grams of potassium ferrate and put them in The ball mill is ball milled 4 times in the ball milling tank of the high-energy ball mill. Each time the ball mill is rotated at 450 rpm for 25 minutes and paused for 4 minutes. Finally, the intermediate product is obtained after standing for 70 minutes;

B. Place the intermediate product in a carbonization furnace, treat it at 180°C for 2 hours in an air atmosphere, and then perform a carbonization reaction in a nitrogen atmosphere. During the carbonization reaction, nitrogen is continuously introduced at a rate of 25 mL/min. First, start at room temperature. Raise the temperature to 300°C at a rate of 1.2°C/min, then increase the temperature to 850°C at a rate of 2.2°C/min, hold it for 3.5 hours, and then lower it to room temperature to obtain a black nitrogen-, phosphorus-, and iron-doped carbon material.

The parameters of the prepared carbon material are as follows: specific surface area 689 m ² /g, particle size distribution 23-47nm.

Effect example 1

The carbon materials prepared in Examples 1-3 were used to prepare rubber waterstop samples 1 to 3 through the following methods:

Put 100kg of butyl rubber into the internal mixer to break the rubber, mash for 30 seconds, and lift the plug; add 40kg of nitrogen, phosphorus, and iron-doped carbon materials into the internal mixer, mix for one stage, and mix for 2 minutes, and then add 5kg of ZnO, 1kg of stearic acid is added together, the mixing time is maintained for about 6 minutes, the temperature is about 140°C, and the glue is discharged after 90 seconds; then adjust the roller distance of the open mill, pour the glue 3 times, then remove the tablets, and cool to room temperature;

Then mix 2kg of sulfur and 1kg of accelerator on the open mill for two-stage mixing, pass through, triangular bag and roll three times each, and remove the pieces; put the mixed rubber into the mold and vulcanize to form the rubber sample, as described The vulcanization temperature is 145°C, the vulcanization time is 180s, and the vulcanization pressure is 10MPa; the accelerator is dibenzothiazole disulfide (DM) and N-cyclohexyl-2-benzene with a mass ratio of 1:0.5:0.2:2:0.2 Thiazole hypoxanthamide (CZ), thiuram disulfide (TMTD), dithiodimorpholine (DTDM) and 2-thiol benzothiazole (M).

According to the Q/CR 562.2-2017 "Railway Tunnel Anti-Drainage Materials Part 2: Waterstop" standard, the performance of the obtained Samples 1 to 3 was tested. The results are as follows in Table 1:

Table 1

Comparative example 1

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

A. Take 5 grams of chitosan, 2 grams of disodium hydrogen phosphate, 2 grams of (ethane-1,2-diylbis(phosphine))tetramethanol, 2 grams of zinc chloride and 3 grams of potassium ferrate and put it in Mill the ball three times in the ball milling tank of the high-energy ball mill. Each time, the ball mill rotates at 500 rpm for 20 minutes and pauses for 5 minutes. Finally, the intermediate product is obtained after standing for 1 hour;

B. Place the intermediate product in a carbonization furnace, treat it at 200°C for 3 hours in an air atmosphere, and then perform a carbonization reaction in a nitrogen atmosphere. During the carbonization reaction, nitrogen gas is continuously introduced at a rate of 20 mL/min. Start with The room temperature is raised to 300°C at a rate of 1.5°C/min, then raised to 900°C at a rate of 2.0°C/min, kept for 3 hours, and then lowered to room temperature to obtain black nitrogen, phosphorus, and iron-doped carbon materials. .

The parameters of the prepared carbon material are as follows: specific surface area 433m ² /g, particle size distribution 39-77nm.

Comparative example 2

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

A. Take 5 grams of chitosan, 2 grams of diammonium hydrogen citrate, 2 grams of (ethane-1,2-diylbis(phosphine))tetramethanol, 2 grams of zinc chloride and 3 grams of potassium ferrate. Put it into the ball milling tank of a high-energy ball mill and ball mill it three times. Each time, the ball mill rotates at 500 rpm for 20 minutes and pauses for 5 minutes. Finally, the intermediate product is obtained after standing for 1 hour;

B. Place the intermediate product in a carbonization furnace, treat it at 200°C for 3 hours in an air atmosphere, and then perform a carbonization reaction in a nitrogen atmosphere. During the carbonization reaction, nitrogen gas is continuously introduced at a rate of 20 mL/min. Start with The room temperature is raised to 300°C at a rate of 1.5°C/min, then raised to 900°C at a rate of 2.0°C/min, kept for 3 hours, and then lowered to room temperature to obtain black nitrogen, phosphorus, and iron-doped carbon materials. .

The parameters of the prepared carbon material are as follows: specific surface area 490m ² /g, particle size distribution 35-64nm.

Comparative example 3

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

A. Take 5 grams of chitosan, 2 grams of aluminum dihydrogen phosphate, 2 grams of (ethane-1,2-diylbis(phosphine))tetramethanol, 2 grams of zinc chloride and 3 grams of potassium ferrate and put it in Mill the ball three times in the ball milling tank of the high-energy ball mill. Each time, the ball mill rotates at 500 rpm for 20 minutes and pauses for 5 minutes. Finally, the intermediate product is obtained after standing for 1 hour;

B. Place the intermediate product in a carbonization furnace, treat it at 200°C for 3 hours in an air atmosphere, and then perform a carbonization reaction in a nitrogen atmosphere. During the carbonization reaction, nitrogen gas is continuously introduced at a rate of 20 mL/min. Start with The room temperature is raised to 300°C at a rate of 1.5°C/min, then raised to 900°C at a rate of 2.0°C/min, kept for 3 hours, and then lowered to room temperature to obtain black nitrogen, phosphorus, and iron-doped carbon materials. .

The parameters of the prepared carbon material are as follows: specific surface area 512m ² /g, particle size distribution 28-81nm.

Comparative example 4

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

A. Take 5 grams of chitosan, 2 grams of di(tetrabutylammonium) dihydrogen pyrophosphate, 2 grams of (ethane-1,2-diylbis(phosphine))tetramethanol, 2 grams of zinc chloride and Put 3 grams of potassium ferrate into the ball milling tank of a high-energy ball mill and ball mill three times. Each time, the ball mill rotates at 500 rpm for 20 minutes and pauses for 5 minutes. Finally, the intermediate product is obtained after standing for 1 hour;

B. Place the intermediate product in a carbonization furnace, treat it at 200°C for 3 hours in an air atmosphere, and then perform a carbonization reaction in a nitrogen atmosphere. During the carbonization reaction, nitrogen gas is continuously introduced at a rate of 20 mL/min. Start with The room temperature is raised to 300°C at a rate of 1.5°C/min, then raised to 900°C at a rate of 2.0°C/min, kept for 3 hours, and then lowered to room temperature to obtain black nitrogen, phosphorus, and iron-doped carbon materials. .

The parameters of the prepared carbon material are as follows: specific surface area 525m ² /g, particle size distribution 24-76nm.

Comparative example 5

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

A. Take 5 grams of chitosan, 2 grams of diammonium hydrogen phosphate, 2 grams of 1,2-bis(diethylphosphorus)ethane, 2 grams of zinc chloride and 3 grams of potassium ferrate and put them into the ball milling tank of the high-energy ball mill. Ball mill three times, each time the ball mill is rotated at 500 rpm for 20 minutes, paused for 5 minutes, and finally left to stand for 1 hour to obtain the intermediate product;

B. Place the intermediate product in a carbonization furnace, treat it at 200°C for 3 hours in an air atmosphere, and then perform a carbonization reaction in a nitrogen atmosphere. During the carbonization reaction, nitrogen gas is continuously introduced at a rate of 20 mL/min. Start with The room temperature is raised to 300°C at a rate of 1.5°C/min, then raised to 900°C at a rate of 2.0°C/min, kept for 3 hours, and then lowered to room temperature to obtain black nitrogen, phosphorus, and iron-doped carbon materials. .

The parameters of the prepared carbon material are as follows: specific surface area 676 m ² /g, particle size distribution 22-49nm.

Comparative example 6

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

A. Take 5 grams of chitosan, 2 grams of diammonium hydrogen phosphate, 2 grams of bis(diethoxyphosphono)acetylene, 2 grams of zinc chloride and 3 grams of potassium ferrate, put them into the ball milling tank of a high-energy ball mill and grind them three times. , each time the ball mill is rotated at 500 rpm for 20 minutes, paused for 5 minutes, and finally left to stand for 1 hour to obtain the intermediate product;

B. Place the intermediate product in a carbonization furnace, treat it at 200°C for 3 hours in an air atmosphere, and then perform a carbonization reaction in a nitrogen atmosphere. During the carbonization reaction, nitrogen gas is continuously introduced at a rate of 20 mL/min. Start with The room temperature is raised to 300°C at a rate of 1.5°C/min, then raised to 900°C at a rate of 2.0°C/min, kept for 3 hours, and then lowered to room temperature to obtain black nitrogen, phosphorus, and iron-doped carbon materials. .

The parameters of the prepared carbon material are as follows: specific surface area 659m ² /g, particle size distribution 24-52nm.

Comparative example 7

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

Take 5 grams of chitosan, 2 grams of diammonium hydrogen phosphate, 2 grams of tetraethylammonium tetrafluoroborate, 2 grams of zinc chloride and 3 grams of potassium ferrate, put them into the ball milling tank of a high-energy ball mill, and grind them three times. Rotate at 500 rpm for 20 minutes, pause for 5 minutes, and finally wait for 1 hour to obtain the intermediate product;

B. Place the intermediate product in a carbonization furnace, treat it at 200°C for 3 hours in an air atmosphere, and then perform a carbonization reaction in a nitrogen atmosphere. During the carbonization reaction, nitrogen gas is continuously introduced at a rate of 20 mL/min. Start with The room temperature is raised to 300°C at a rate of 1.5°C/min, then raised to 900°C at a rate of 2.0°C/min, kept for 3 hours, and then lowered to room temperature to obtain black nitrogen, phosphorus, and iron-doped carbon materials. .

The parameters of the prepared carbon material are as follows: specific surface area 585m ² /g, particle size distribution 22-71nm.

Comparative example 8

A method for preparing nitrogen-, phosphorus-, and iron-doped carbon materials, including the following steps:

A. Take 5 grams of chitosan, 2 grams of diammonium hydrogen phosphate, 2 grams of tricyclohexylphosphine fluoroborate, 2 grams of zinc chloride and 3 grams of potassium ferrate, put them into the ball milling tank of a high-energy ball mill and grind them three times. The ball mill is rotated at 500 rpm for 20 minutes, paused for 5 minutes, and finally left to stand for 1 hour to obtain the intermediate product;

B. Place the intermediate product in a carbonization furnace, treat it at 200°C for 3 hours in an air atmosphere, and then perform a carbonization reaction in a nitrogen atmosphere. During the carbonization reaction, nitrogen gas is continuously introduced at a rate of 20 mL/min. Start with The room temperature is raised to 300°C at a rate of 1.5°C/min, then raised to 900°C at a rate of 2.0°C/min, kept for 3 hours, and then lowered to room temperature to obtain black nitrogen, phosphorus, and iron-doped carbon materials. .

The parameters of the prepared carbon material are as follows: specific surface area 591m ² /g, particle size distribution 23-73nm.

Effect example 2

The nitrogen-, phosphorus-, and iron-doped carbon materials prepared in Examples 1-8 were used to prepare rubber waterstops Comparative Sample 1-Comparative Sample 8 through the following methods:

Preparation method of rubber waterstop:

Put 100kg of butyl rubber into the internal mixer to break the rubber, mash for 30 seconds, and lift the plug; add 40kg of nitrogen, phosphorus, and iron-doped carbon materials into the internal mixer, mix for one stage, and mix for 2 minutes, and then add 5kg of ZnO, 1kg of stearic acid is added together, the mixing time is maintained for about 6 minutes, the temperature is about 140°C, and the glue is discharged after 90 seconds; then adjust the roller distance of the open mill, pour the glue 3 times, then remove the tablets, and cool to room temperature;

Then mix 2kg of sulfur and 1kg of accelerator on the open mill for two-stage mixing, pass through, triangular bag and roll three times each, and remove the pieces; put the mixed rubber into the mold and vulcanize to form the rubber sample, as described The vulcanization temperature is 145°C, the vulcanization time is 180s, and the vulcanization pressure is 10MPa; the accelerator is dibenzothiazole disulfide (DM) and N-cyclohexyl-2-benzene with a mass ratio of 1:0.5:0.2:2:0.2 Thiazole hypoxanthamide (CZ), thiuram disulfide (TMTD), dithiodimorpholine (DTDM) and 2-thiol benzothiazole (M).

According to the Q/CR 562.2-2017 "Railway Tunnel Anti-Drainage Materials Part 2: Waterstop" standard, the performance of the obtained comparative sample 1-comparative sample 8 was tested. The results are as follows in Table 2:

Table 2

Claims (8)

1. A method for preparing a nitrogen, phosphorus and iron doped carbon material, which is characterized by comprising the following steps:

A. the mass ratio is 3-7: 1-4: 1.5-5.3: 1.3 to 4.1: 2.1-6.4 of chitosan, diammonium hydrogen phosphate, (ethane-1, 2-diyl bis (phosphino)) tetramethanol, zinc chloride and potassium ferrate, and standing to obtain an intermediate product;

B. under the air atmosphere, treating the intermediate product at 180-220 ℃ for 2-4 hours, then placing the intermediate product in an inert atmosphere for carbonization reaction, and cooling to room temperature to obtain a nitrogen, phosphorus and iron doped carbon material;

in the step B, protective gas is continuously introduced at the speed of 15-25 mL/min, the temperature is firstly increased to 300+/-10 ℃ from room temperature at the speed of 1.2-1.7 ℃/min, and then the temperature is increased to 900+/-10 ℃ at the speed of 1.8-2.2 ℃/min, and the temperature is kept for 2.5-3.5 hours.

2. The method for preparing the nitrogen, phosphorus and iron doped carbon material according to claim 1, wherein the mass ratio of chitosan, diammonium phosphate, (ethane-1, 2-diylbis (phosphino)) tetra-methanol, zinc chloride and potassium ferrate in the step a is 5:2:2:2:3.

3. the method for preparing the nitrogen, phosphorus and iron doped carbon material according to claim 1, wherein the ball milling step of the step A is performed for 15-25min, and is stopped for 4-6min, and repeated for 2-4 times.

4. The method for preparing the nitrogen, phosphorus and iron doped carbon material according to claim 1, wherein the ball milling speed of the step A is 450-550 rpm.

5. The method for preparing a nitrogen, phosphorus and iron doped carbon material according to claim 1, wherein the standing step is specifically standing for 50-70min.

6. The method for preparing a nitrogen, phosphorus and iron doped carbon material according to claim 1, wherein the viscosity of the chitosan is 200-400mpa.s.

7. Use of a nitrogen, phosphorus, iron doped carbon material obtained by the preparation method according to any one of claims 1-6 in the rubber field.

8. Use according to claim 7, of the nitrogen, phosphorus, iron doped carbon material for the preparation of rubber water stops.