CN105347326A - Preparation method of carbon nano-gourd-shaped structure materials - Google Patents

Abstract

Preparation method of carbon nano-gourd-shaped structure materials comprises the following steps: (1) placing a carrier such as a ceramic boat or a quartz boat and catalyst in a tube furnace, heating the carrier to a temperature of 800-1200 DEGC in a buffer gas atmosphere and under a normal pressure; (2) keeping the temperature in the range of 800-1200 DEG C, feeding and enabling the buffer gas to pass through precursors and then to the tube furnace, depositing carbon nano-gourd-shaped structure materials on the carrier such as the ceramic boat or the quartz boat for 1-30 minutes; and (3) stopping feeding the buffer gas passing through the precursors, cooling the precursor in the buffer gas to a room temperature. The preparation method of the invention is simple, has a low energy consumption, and high product purity, and can be industrialized; the prepared carbon nano-gourd-shaped structure materials has advantages of big surface area and good binding with a substrate, and can be directly used in physical property detections and applied in all kinds of products.

Description

A kind of preparation method of carbon nano gourd structure material

technical field

The invention belongs to the field of functional materials and relates to a preparation method of carbon nanostructure materials.

Background technique

Carbon nanomaterials refer to carbon materials with at least one dimension of the dispersed phase smaller than 100nm. The dispersed phase can consist of either carbon atoms or non-carbon atoms. The carbon nanomaterials most reported in the literature are carbon nanotubes. Since Iijima of Japan discovered carbon nanotubes in 1991, due to their unique one-dimensional structure, physical and chemical properties and potential application prospects, they have always attracted the attention of scientists in the fields of physical chemistry and materials science all over the world. Carbon nanotubes are hollow, seamless "microtubes" formed by single-layer or multi-layer graphite sheets wound around the central axis at a certain helical angle. Each layer consists of one carbon atom hybridized with three surrounding carbon atoms through ^sp2 A cylindrical surface composed of hexagons formed by fully bonded carbon atoms.

The application research of carbon nanomaterials mainly involves medical sensing materials (biosensors, etc.), energy storage materials (lithium batteries, supercapacitors and other electrochemical energy storage, etc.), energy conversion materials (fuel cells, etc.), environmental detection and repair Materials (applied to chemical and physical sensing materials, adsorption materials, etc.). At present, the main synthesis methods of carbon nanomaterials are arc method, chemical vapor deposition (CVD) method, solid phase pyrolysis method and laser method, etc. Among them, the chemical vapor deposition (CVD) method is not only simple in preparation method, easy to control the process conditions, and the raw materials Cheap, suitable for large-scale production and other advantages, the resulting product has low impurity content and high degree of graphitization, so it has become the main method for preparing carbon nanomaterials. Due to the different control conditions, in addition to the usual linear tubular carbon nanostructures, many other shapes of carbon nanotubes have also been obtained. Due to the unique morphology and structural features, it has special properties.

The carbon nano gourd structure is a coaxial cone. The cone is composed of concentric cylindrical graphite layers gradually shortened along the outer surface. The innermost layer of the cone is a single-wall nanometer with a diameter of one or several nanometers. Carbon tubes or multi-walled carbon nanotubes, they are either directly superimposed by carbon nanotubes of different layers or structures through van der Waals force, or stacked in bundles of carbon nanotubes with the same layer number, each part is composed of carbon nanotubes form a whole in a seamless manner. The ladder structure composed of gradually shortened graphite layers on the outer surface of these carbon nano gourd structure materials is a large number of active sites, which can be used as an excellent carrier for catalysts or ions. In the field of catalyst industry and electrochemical power energy (such as high-performance lithium ion Batteries and supercapacitors) have broad application development prospects. Compared with single-wall carbon nanotubes, the cone structure not only greatly enhances its radial mechanical strength, but also has a top size within a few nanometers, which is an ideal tip and field emission material for scanning probes. In addition, the carbon nano gourd structure has several nanometers and independent inner diameters, which can be used as multiple independent channels for storing and transporting different liquid substances at the same time, and even made into independent composite nano-injectors for nano-level cell repair and Modification research, which has been widely used in the fields of biology and chemistry. Furthermore, compared with the smooth carbon nanotubes, the new carbon nanostructures with a gourd-like structure are obviously better reinforcements in the field of super composite materials. In addition, this new type of carbon nano gourd structure, as a carbon whole, will most likely promote the development of all-carbon nanomaterial electronic devices because of the excellent electrical, optical and mechanical properties of carbon nanotubes.

Contents of the invention

The purpose of the present invention is to provide a method for preparing carbon nano gourd structural materials, which has the advantages of simple equipment, easy operation, low energy consumption, and high product purity.

The present invention is achieved through the following technical solutions.

The preparation method of the carbon nano gourd structural material according to the present invention is as follows.

(1) Put the ceramic boat or quartz boat and other carrier and catalyst into the tube furnace, and raise the temperature to 800-1200℃ in the buffer gas atmosphere under normal pressure.

(2) Maintain a temperature of 800-1200°C, feed buffer gas, the buffer gas passes through the precursor and then enters the tube furnace, and deposits carbon nano-cucurbit structure materials on carriers such as ceramic boats or quartz boats, and the growth time is 1-30min.

(3) Turn off the buffer gas passing through the precursor, and cool to room temperature in the buffer gas.

The buffer gas described in the step (1) of the present invention is a mixed gas of one or more of hydrogen, argon, and nitrogen; the catalyst is ferrocene, nickelocene or cobaltocene;

The heating rate in step (1) of the present invention is 20-40° C./min.

The precursor described in the step (2) of the present invention is formed by adding a growth promoter to a carbon source, wherein the carbon source is a carbon-containing organic molecule, such as benzene, methane, acetylene, ethanol, etc.; the growth promoter The sulfur-containing growth promoter can be thiophene, carbon disulfide or hydrogen sulfide; the volume ratio of carbon source and growth promoter in the precursor is 1/500-1/5.

The flow rate of the buffer gas passing through the precursor in step (2) of the present invention is 10-500 sccm/s.

The present invention has the following beneficial effects.

(1) The preparation process of the present invention is simple, the energy consumption is low, and the product has high purity and can be produced on a large scale.

(2) The gourd-shaped carbon nanomaterial prepared in the present invention has the advantages of large surface area, easy to combine well with the matrix, and the like.

(3) The present invention uses sulfur-containing chemicals as growth promoters, which can improve the formation of carbon nano-cucurbit structural materials.

(4) The present invention can control the length of gourd-shaped carbon nanomaterials by adjusting various experimental parameters such as growth time, flow rate of carbon source gas, etc.

(5) The carbon nano gourd structure material obtained in the present invention can be directly used for physical property detection and applied to various application products.

Description of drawings

Fig. 1 is a schematic structural diagram of an experimental device for preparing gourd-shaped carbon nanomaterials.

FIG. 2 is a field emission scanning electron microscope image (SEM image) of the gourd-shaped carbon nanomaterial prepared in Example 1. FIG.

FIG. 3 is a transmission electron microscope image (TEM image) of the gourd-shaped carbon nanomaterial prepared in Example 1. FIG.

FIG. 4 is a transmission electron microscope image (TEM image) of the gourd-shaped carbon nanomaterial prepared in Example 2. FIG.

detailed description

The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.

The methods described in the following examples, unless otherwise specified, are conventional methods; the materials and reagents, unless otherwise specified, can be obtained from commercial sources.

Example 1.

The precursor is mixed with 100ml benzene and 10% thiophene. The experimental device used is shown in Figure 1. Carriers such as ferrocene, ceramic boats or quartz boats are placed in the tube furnace quartz tube at the position shown in the figure. Under normal pressure, the hydrogen flow rate is 180 sccm and the precursor The hydrogen flow rate of the body was 100 sccm for exhausting for 2 minutes, then the carbon source was turned off, and then the temperature was raised at 27.5°C/s. When the temperature reaches 1100°C, adjust the hydrogen flux to 30 sccm, and at the same time pass through the precursor hydrogen flow rate of 50 sccm, by moving the quartz tube, move the ferrocene into the quartz tube, keep at 1100°C for 10 minutes, and then close the precursor and adjust the hydrogen flow rate as a buffer gas to 180 sccm, move the ferrocene back to its original position by moving the quartz tube, and cool down to room temperature to obtain gourd-shaped carbon nanomaterials. The SEM and TEM images of the obtained gourd-shaped carbon nanomaterial are shown in Fig. 2 and Fig. 3 .

Example 2.

The precursor is mixed with 100ml benzene and 20% thiophene. The experimental device used is shown in Figure 1. Carriers such as ferrocene, ceramic boats or quartz boats are placed in the tube furnace quartz tube at the position shown in the figure. Under normal pressure, the hydrogen flow rate is 180 sccm and the precursor The hydrogen flow rate of the body was 100 sccm for exhausting for 2 minutes, then the carbon source was turned off, and then the temperature was raised at 27.5°C/s. When the temperature reaches 1100°C, adjust the hydrogen flux to 50 sccm, and at the same time pass through the hydrogen flow rate of 50 sccm through the precursor, move the quartz tube to move the ferrocene into the quartz tube, keep it at 1100°C for 20 minutes, and then turn off the flow through the precursor and adjust the flow rate of hydrogen as a buffer gas to 180 sccm, move the ferrocene back to its original position by moving the quartz tube, and cool down to room temperature to obtain gourd-shaped carbon nanomaterials. The SEM image of the obtained gourd-shaped carbon nanomaterial is shown in FIG. 4 .

Example 3.

The precursor is mixed with 100ml benzene and 30% thiophene. The experimental device used is shown in Figure 1. Carriers such as ferrocene, ceramic boats or quartz boats are placed in the tube furnace quartz tube at the position shown in the figure. Under normal pressure, the hydrogen flow rate is 180 sccm and the precursor The hydrogen flow rate of the body was 100 sccm for exhausting for 2 minutes, then the carbon source was turned off, and then the temperature was raised at 27.5°C/s. When the temperature reaches 1150°C, adjust the hydrogen flow rate to 100 sccm, and at the same time pass through the precursor hydrogen flow rate of 200 sccm, move the quartz tube to move the ferrocene into the quartz tube, keep it at 1100°C for 10 minutes, and then turn off the flow through the precursor and adjust the flow rate of hydrogen as a buffer gas to 180 sccm, move the ferrocene back to its original position by moving the quartz tube, and cool down to room temperature to obtain gourd-shaped carbon nanomaterials. Figure 2.

Example 4.

The precursor is made by mixing 100ml absolute ethanol and 10% thiophene. The experimental device used is shown in Figure 1. Carriers such as ferrocene, ceramic boats or quartz boats are placed in the tube furnace quartz tube at the position shown in the figure. Under normal pressure, the hydrogen flow rate is 180 sccm and the precursor The hydrogen flow rate of the body was 100 sccm for exhausting for 2 minutes, then the carbon source was turned off, and then the temperature was raised at 25°C/s. When the temperature reaches 1100°C, adjust the hydrogen flux to 20sccm, and at the same time pass through the precursor hydrogen flow rate of 60sccm, move the quartz tube to move the ferrocene into the quartz tube, keep it at 1100°C for 10min, then turn off the flow through the precursor and adjust the hydrogen flow rate as a buffer gas to 180 sccm, move the ferrocene back to its original position by moving the quartz tube, and cool down to room temperature to obtain gourd-shaped carbon nanomaterials.

Example 5.

The precursor is made by mixing 100ml absolute ethanol and 30% thiophene. The experimental device used is shown in Figure 1. Carriers such as ferrocene, ceramic boats or quartz boats are placed in the tube furnace quartz tube at the position shown in the figure. Under normal pressure, the hydrogen flow rate is 180 sccm and the precursor The hydrogen flow rate of the body was 100 sccm for exhausting for 2 minutes, then the carbon source was turned off, and then the temperature was raised at 30°C/s. When the temperature reaches 1050°C, adjust the hydrogen flux to 40 sccm, and at the same time pass through the hydrogen flow rate of 120 sccm through the precursor, move the quartz tube to move the ferrocene into the quartz tube, keep it at 1050°C for 5 minutes, and then turn off the flow through the precursor and adjust the hydrogen flow rate as a buffer gas to 180 sccm, move the ferrocene back to its original position by moving the quartz tube, and cool down to room temperature to obtain gourd-shaped carbon nanomaterials.

Claims (6)

1. a preparation method of carbon nano gourd structure material, is characterized in that according to the following steps: (1) Put the ceramic boat or quartz boat and the catalyst into the tube furnace, and raise the temperature to 800-1200°C in the buffer gas atmosphere under normal pressure; (2) Maintain a temperature of 800-1200°C, feed buffer gas, the buffer gas passes through the precursor and then feeds into the tube furnace, and deposits carbon nano gourd structure materials on ceramic boats or quartz boats, and the growth time is 1-30min; (3) Turn off the buffer gas passing through the precursor, and cool to room temperature in the buffer gas; The buffer gas in step (1) is one or more mixed gases of hydrogen, argon, and nitrogen; the catalyst is ferrocene, nickelocene or cobaltocene; The precursor described in step (2) is formed by adding a growth promoter to a carbon source, wherein the carbon source is a carbon-containing organic molecule; the growth promoter is a sulfur-containing growth promoter. 2. The method for preparing carbon nano-cucurbit structure material according to claim 1, characterized in that the heating rate in step (1) is 20-40°C/min. 3. The preparation method of carbon nano-cucurbit structure material according to claim 1, characterized in that the volume ratio of carbon source and growth promoter in the precursor in step (2) is 1/500-1/5. 4. The method for preparing carbon nano-cucurbit structural materials according to claim 1, characterized in that the flow rate of the buffer gas passing through the precursor in step (2) is 10-500 sccm/s. 5. The method for preparing carbon nano-cucurbit structure material according to claim 1, characterized in that the carbon-containing organic molecule in step (2) is benzene, methane, acetylene or ethanol. 6 . The preparation method of carbon nano gourd structure material according to claim 1 , characterized in that the sulfur-containing growth promoter in step (2) is thiophene, carbon disulfide or hydrogen sulfide.