CN113651313B

CN113651313B - Hollow submicron nitrogen-doped carbon tube and preparation method thereof

Info

Publication number: CN113651313B
Application number: CN202111140565.6A
Authority: CN
Inventors: 谢阿明; 陈佑剑; 焦颖芝
Original assignee: Shaoxing Daopu New Material Technology Co ltd
Current assignee: Shaoxing Daopu New Material Technology Co ltd
Priority date: 2021-09-28
Filing date: 2021-09-28
Publication date: 2023-06-06
Anticipated expiration: 2041-09-28
Also published as: CN113651313A

Abstract

The invention belongs to the technical field of material preparation, and in particular relates to a preparation method of a hollow submicron nitrogen-doped carbon tube, which comprises the following steps: step 1, dissolving small organic molecules in an organic solvent to obtain a solution A, and dispersing a surfactant into deionized water to obtain a solution B; dropwise adding the solution A into the solution B while stirring to obtain a self-assembled organic structure; step 2, adding the self-assembled organic structure into a pH=8.5 Tris buffer solution for ultrasonic dispersion, and then adding dopamine for stirring reaction to obtain a self-assembled organic structure wrapped by polydopamine; and step 3, placing the self-assembled organic structure coated by the polydopamine in a tube furnace for high-temperature calcination to obtain the hollow submicron nitrogen-doped carbon tube. The invention solves the blank of hollow submicron carbon tube, and forms a controllable self-assembled organic structure by using organic micromolecules and dopamine, thereby forming the hollow carbon tube with large specific surface area.

Description

Hollow submicron nitrogen-doped carbon tube and preparation method thereof

Technical Field

The invention belongs to the technical field of material preparation, and particularly relates to a hollow submicron nitrogen-doped carbon tube.

Background

Carbon materials are emerging materials with excellent performance, simple preparation and low cost, and more reports on the preparation and performance research of the carbon materials are also in recent years. Among various carbon nanomaterial, hollow carbon nanostructure has attracted attention because of its high thermal stability, strong electron transfer ability, large specific surface area, abundant exposed active sites, and flexible shape and structure. A great deal of research shows that the hollow carbon nano structure has excellent performance in the aspects of energy sources, catalysis, electronics, biomedicine and the like.

However, pure carbon materials have certain limitations in practical application. Heteroatom doping can effectively adjust the physicochemical properties of the carbon material. Among the numerous heteroatoms, nitrogen-doped carbon materials are well formed due to the close radii of the nitrogen and carbon atoms. The nitrogen atom doping has important influence on the aspects of conductivity, field emission performance, super capacitor performance, oxygen reduction catalytic performance, other catalytic performances, hydrogen storage performance and the like of the carbon material. In recent years, the preparation of nitrogen-doped carbon materials and the performance research thereof have been hot spots in the field of carbon material research in recent years, and have received extensive attention from researchers at home and abroad.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a preparation method of a hollow submicron nitrogen-doped carbon tube, which solves the problem of blank hollow submicron carbon tubes, and forms a controllable self-assembled organic structure by using small organic molecules and dopamine, so that the hollow carbon tube with large specific surface area is formed, and the preparation method is simple and low in cost.

In order to achieve the technical purpose, the technical scheme of the invention is as follows:

a preparation method of a hollow submicron nitrogen-doped carbon tube comprises the following steps:

step 1, dissolving small organic molecules in an organic solvent to obtain a 5mg/mL solution A, and dispersing a surfactant into deionized water to obtain a 25mg/L solution B; dropwise adding the solution A into the solution B while stirring, wherein the volume ratio of the solution A to the solution B is 1:7, standing, filtering and drying to obtain a self-assembled organic structure after the reaction is finished;

step 2, adding 50mg of the self-assembled organic structure into a Tris buffer solution with pH of 8.5 for ultrasonic dispersion, and then adding dopamine for stirring reaction; filtering, washing and drying after the reaction is finished to obtain a self-assembled organic structure wrapped by polydopamine;

and step 3, placing the self-assembled organic structure coated by the polydopamine in a tube furnace, calcining at high temperature under the protection of argon, and obtaining the hollow submicron nitrogen-doped carbon tube after the reaction is finished.

Wherein, the small organic molecules in the step 1 adopt anthracene, 9, 10-dinitrile anthracene or 9, 10-dibromoanthracene.

The organic solvent in the step 1 adopts one or more of ethanol, ethyl acetate, methylene dichloride, normal hexane and toluene.

The surfactant in the step 1 adopts one of sodium dodecyl sulfate, cetyltrimethylammonium bromide and sodium dodecyl benzene sulfonate.

Preferably, the mass of the dopamine in the step 2 is 10-100mg.

Preferably, the stirring reaction time in the step 2 is 6-24h.

Preferably, the calcination temperature in the step 3 is 500-1000 ℃.

Preferably, the calcination time in the step 3 is 1 to 12 hours.

From the above description, it can be seen that the present invention has the following advantages:

1. the invention solves the blank of hollow submicron carbon tube, and forms a controllable self-assembled organic structure by using small organic molecules and dopamine, thereby forming the hollow carbon tube with large specific surface area.

2. The invention utilizes the concentration of small organic molecules to control the microscopic dimension of the self-assembled structure, thereby achieving the purpose of controlling the microscopic dimension of the hollow submicron nitrogen-doped carbon tube.

3. According to the invention, the thickness of the tube wall of the hollow submicron nitrogen-doped carbon tube is realized by using the concentration of dopamine, so that the preparation controllability of the carbon tube is improved, and the yield is improved.

Drawings

FIG. 1 is a scanning electron micrograph of the self-assembled organic structure of example 1;

FIG. 2 is a scanning electron micrograph of a self-assembled organic structure coated with polydopamine of example 3

Fig. 3 is a transmission electron micrograph of a hollow submicron nitrogen doped carbon tube in example 4.

Detailed Description

One embodiment of the present invention will be described in detail with reference to fig. 1 to 3, but does not limit the claims of the present invention in any way.

Example 1

The preparation method of the hollow submicron nitrogen-doped carbon tube specifically comprises the following steps:

step 1: 60mg of 9, 10-dinitrile anthracene is weighed and dissolved in 12mL of ethanol to obtain a solution A; 20mg of sodium dodecyl sulfate was weighed and dissolved in 800mL of deionized water to obtain solution B. Dropwise adding the solution A into the solution B while stirring, wherein the volume ratio of the solution A to the solution B is 1:7, reacting for 10min, standing, filtering and drying to obtain a self-assembled organic structure, as shown in figure 1;

step 2: 50mg of the self-assembled organic structure was weighed and dissolved in 200mL of pH=8.5 Tris buffer solution and dispersed by sonication. Then 10mg of dopamine was added and the reaction was stirred for 6h. Filtering, washing and drying to obtain a self-assembled organic structure coated by polydopamine;

step 3: and placing the self-assembled organic structure coated by polydopamine in a tube furnace, and heating to 500 ℃ under argon to calcine for 1h to obtain the hollow submicron nitrogen-doped carbon tube sample 1.

Example 2

The procedure of example 1 was followed except that the "calcination at 500℃for 1 hour" in step 3 of example 1 was changed to "calcination at 1000℃for 12 hours", and the remaining steps were the same as in example 1, to obtain a hollow submicron nitrogen-doped carbon tube sample 2. The scanning electron microscope finds that the width surface of the obtained hollow submicron nitrogen-doped carbon tube is smoother, which indicates that the increase of carbonization temperature and the prolongation of carbonization time are favorable for the formation of graphitized structures.

Example 3

step 1: 30mg of 9, 10-dibromoanthracene is weighed and dissolved in 12mL of dichloromethane to obtain a solution A; 20mg of cetyltrimethylammonium bromide was weighed and dissolved in 800mL of deionized water to give solution B. Dropwise adding the solution A into the solution B while stirring, wherein the volume ratio of the solution A to the solution B is 1:7, reacting for 10min, standing, filtering and drying to obtain the self-assembled organic structure.

Step 2: 50mg of the self-assembled organic structure was weighed and dissolved in 200mL of pH=8.5 Tris buffer solution and dispersed by sonication. 50mg of dopamine was then added and the reaction stirred for 12h. Filtering, washing and drying to obtain the self-assembled organic structure coated by polydopamine, as shown in figure 2.

Step 3: and placing the self-assembled organic structure coated by polydopamine in a tube furnace, and heating to 700 ℃ under argon to calcine for 6 hours to obtain the hollow submicron nitrogen-doped carbon tube sample 3.

Example 4

step 1: 30mg of anthracene is weighed and dissolved in 12mL of toluene to obtain a solution A; 10mg of sodium dodecyl benzene sulfonate was weighed and dissolved in 800mL of deionized water to obtain solution B. Dropwise adding the solution A into the solution B while stirring, wherein the volume ratio of the solution A to the solution B is 1:7, reacting for 10min, standing, filtering and drying to obtain the self-assembled organic structure.

Step 2: 50mg of the self-assembled organic structure was weighed and dissolved in 200mL of pH=8.5 Tris buffer solution and dispersed by sonication. 100mg of dopamine was then added and the reaction stirred for 24h. Filtering, washing and drying to obtain the self-assembled organic structure coated by polydopamine.

Step 3: the self-assembled organic structure coated by polydopamine is placed in a tube furnace, and the temperature is raised to 800 ℃ under argon for calcination for 4 hours, so that a hollow submicron nitrogen-doped carbon tube sample 4 is prepared, as shown in figure 3.

Example 5

The procedure of example 4 was followed except that the "stirring reaction 6h" in step 2 of example 5 was changed to "stirring reaction 24h", and the hollow submicron nitrogen-doped carbon tube sample 5 was obtained. The transmission electron microscope finds that the wall thickness of the obtained hollow submicron nitrogen-doped carbon tube is thickened, which indicates that increasing the dopamine polymerization time is beneficial to improving the wall thickness of the hollow submicron nitrogen-doped carbon tube.

In summary, the invention has the following advantages:

the hollow submicron nitrogen-doped carbon tube is obtained by taking a self-assembled organic structure as a template, taking dopamine as a carbon source and a nitrogen source and performing self-assembly, surface modification and high-temperature carbonization. And experimental tests prove that the hollow submicron nitrogen-doped carbon tube has the inner diameter of 10-500nm, the thickness of 5-20nm and the length of 5-10 mu m.

The preparation method of the invention comprises the following steps: self-assembling organic micromolecules serving as raw materials in a water-organic mixed system to form a self-assembled organic structure, and taking the self-assembled organic structure as a template; carrying out surface modification on the self-assembled template by using a dopamine modification technology to obtain a self-assembled organic structure coated by polydopamine; and (3) carbonizing the self-assembled organic structure coated by polydopamine at high temperature to obtain the hollow submicron nitrogen-doped carbon tube.

The invention has simple reaction and easy treatment; the raw materials are cheap and recyclable, no harmful substances are produced, and the method is economical and environment-friendly. The preparation process is simple, and the prepared hollow submicron nitrogen-doped carbon tube has uniform morphology and larger specific surface area.

It is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those of ordinary skill in the art that the present invention may be modified or substituted for elements thereof to achieve the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.

Claims

1. A preparation method of a hollow submicron nitrogen-doped carbon tube is characterized by comprising the following steps: the method comprises the following steps:

step 1, dissolving small organic molecules in an organic solvent to obtain a solution A, and dispersing a surfactant into deionized water to obtain a solution B; dropwise adding the solution A into the solution B while stirring, standing, filtering and drying to obtain a self-assembled organic structure after the reaction is finished;

step 2, adding the 50mg self-assembled organic structure into a Tris buffer solution with pH of 8.5 for ultrasonic dispersion, and then adding dopamine for stirring reaction; filtering, washing and drying after the reaction is finished to obtain a self-assembled organic structure wrapped by polydopamine;

step 3, placing the self-assembled organic structure coated by polydopamine in a tube furnace, calcining at high temperature under the protection of argon, and obtaining a hollow submicron nitrogen-doped carbon tube after the reaction is finished;

wherein, the small organic molecules in the step 1 adopt anthracene, 9, 10-dinitrile anthracene or 9, 10-dibromoanthracene; the surfactant is one of sodium dodecyl sulfate, cetyltrimethylammonium bromide and sodium dodecyl benzene sulfonate; the mass of the dopamine in the step 2 is 10-100mg.

2. The method for preparing the hollow submicron nitrogen-doped carbon tube according to claim 1, characterized in that: the organic solvent in the step 1 adopts one or more of ethanol, ethyl acetate, methylene dichloride, normal hexane and toluene.

3. The method for preparing the hollow submicron nitrogen-doped carbon tube according to claim 1, characterized in that: the stirring reaction time in the step 2 is 6-24h.

4. The method for preparing the hollow submicron nitrogen-doped carbon tube according to claim 1, characterized in that: the calcination temperature in the step 3 is 500-1000 ℃.

5. The method for preparing the hollow submicron nitrogen-doped carbon tube according to claim 1, characterized in that: the calcination time in the step 3 is 1-12h.

6. A hollow submicron nitrogen-doped carbon tube characterized by: the carbon tube is prepared by the method provided by any one of claims 1-5, and the hollow submicron nitrogen-doped carbon tube has an inner diameter of 10-500nm, a thickness of 5-20nm and a length of 5-10 μm.