CN115340084A - Method for preparing carbon nano tube by hydrogen-free chemical vapor deposition - Google Patents
Method for preparing carbon nano tube by hydrogen-free chemical vapor deposition Download PDFInfo
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- CN115340084A CN115340084A CN202210962506.5A CN202210962506A CN115340084A CN 115340084 A CN115340084 A CN 115340084A CN 202210962506 A CN202210962506 A CN 202210962506A CN 115340084 A CN115340084 A CN 115340084A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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Abstract
The invention relates to the technical field of carbon nanotube preparation, in particular to a method for preparing a carbon nanotube by hydrogen-free chemical vapor deposition, which comprises the following steps: obtaining a cleaned metal substrate, and placing the substrate on a clamp to enable the substrate to be loaded into a reaction furnace of chemical vapor deposition equipment in a vertical posture; preparing a mixed solution containing a catalyst, an alcohol organic matter and a carbon source, and transferring the solution into controllable liquid injection equipment; injecting protective gas into the reaction furnace at a certain flow rate, and heating to 700-900 ℃ under the condition that the injection flow rate of the protective gas is not changed; and injecting the mixed solution into a reaction furnace at a fixed speed by using a liquid injection device to grow the carbon nano tube. Regulating and controlling the growth of the carbon nano tube by adding an alcohol organic matter into a carbon source solution containing a catalyst; the prepared carbon nano tube has high purity and good structural integrity, and presents a net structure on the surface of the substrate, and the tube diameter of the carbon nano tube is thin and long.
Description
Technical Field
The invention belongs to the technical field of carbon nanotube preparation, relates to a carbon nanotube preparation method, and particularly relates to a method for preparing a carbon nanotube by hydrogen-free chemical vapor deposition.
Background
Carbon nanotubes are a novel one-dimensional nanomaterial discovered in the early nineties. The special structure of the carbon nanotube determines the special properties of the carbon nanotube, such as high tensile strength and high thermal stability; the carbon nanotubes may exhibit metallic or semiconducting properties, etc., according to the change in the helical form of the carbon nanotubes. Because the carbon nanotube has an ideal one-dimensional structure and excellent properties in the fields of mechanics, electricity, thermal engineering and the like, the carbon nanotube has a wide application prospect in the fields of interdisciplines such as material science, chemistry, physics and the like, and is also paid more and more attention to scientific research and industrial application.
At the present stage, there are various methods for preparing carbon nanotubes, including arc discharge, laser ablation, and chemical vapor deposition. The chemical vapor deposition method becomes the most common method for preparing the carbon nano tube due to the advantages of easy control of the reaction process, high purity of the obtained material and the like; in the chemical vapor deposition process, the carbon source can be selected from gas or liquid; the protective gas can be argon or nitrogen; hydrogen is a gas used in almost all CVD (chemical vapor deposition) processes. Hydrogen is an important process gas for preparing carbon nanotubes, and can reduce and form catalyst nanoparticles to promote the growth of the carbon nanotubes.
Although hydrogen plays a key role in the preparation of carbon nanotubes, there are also some disadvantages: hydrogen is flammable and explosive, and has safety risk; a tail gas treatment device is required; the cost is relatively high.
Therefore, how to provide a method for preparing carbon nano-particles by hydrogen-free chemical vapor deposition is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
In order to solve the problems of the prior art, the present patent aims to overcome the disadvantages of the prior art, and provides a method for preparing carbon nanotubes, wherein a mixed solution is prepared from an alcohol organic substance and a carbon source solution, so as to realize the preparation of carbon nanotubes under a hydrogen-free condition. Therefore, the safety risk can be reduced, and the safety in preparation is ensured; and unnecessary experimental equipment can be removed, and the cost for preparing the carbon nano tube is reduced.
In order to achieve the above purpose, the invention provides the following technical scheme:
a method for preparing carbon nanotubes by hydrogen-free chemical vapor deposition, comprising the steps of:
1) Placing the cleaned metal substrate on a clamping sheet, and loading the metal substrate into a reaction furnace of chemical vapor deposition equipment in a vertical posture;
2) Preparing a mixed solution containing a catalyst, an alcohol organic matter and a carbon source, and transferring the mixed solution into controllable liquid injection equipment;
3) Injecting protective gas into the reaction furnace in the step 1), and then heating to 200 ℃ for 20 minutes;
4) Under the condition that the injection rate of the protective gas is not changed, continuously heating the reaction furnace, and injecting the mixed solution prepared in the step 2) to grow the carbon nano tube;
5) And stopping injecting the mixed solution after the growth of the carbon nano tube is finished, stopping heating the reaction furnace, and taking out the substrate with the carbon nano tube after the temperature in the furnace is naturally reduced to be below 100 ℃, thus finishing the preparation of the carbon nano tube by hydrogen-free chemical vapor deposition.
Optionally, the metal substrate is selected from two-dimensional or three-dimensional structural metals with a melting point of more than 800 ℃, and is at least one of nickel sheet/foamed nickel, copper sheet/foamed copper, tungsten sheet/foamed tungsten, and titanium sheet/foamed titanium.
Optionally, the alcohol organic matter is at least one selected from methanol, ethanol, propanol and glycol;
the carbon source is organic hydrocarbon and is at least one selected from benzene, pyridine, xylene and dichlorobenzene;
the catalyst is nano-sized metal catalyst particles, and the catalyst is ferrocene.
Furthermore, the volume fraction of the alcohol organic matter is 5-50%, and the injection rate of the mixed solution is 0.005-0.500 ml/min.
Optionally, the protective gas is at least one selected from nitrogen, argon and helium, and the injection flow rate of the protective gas is 100sccm to 3000sccm.
Optionally, in the step 4), the temperature is increased to 700-900 ℃, and the temperature increase rate is 10-40 ℃/min.
Optionally, in the step 5), the time for injecting the mixed solution to perform the carbon nanotube growth is 10 to 180 minutes.
Specifically, in the above method for preparing carbon nanotubes by hydrogen-free chemical vapor deposition, the technical objects/effects generated among the steps are as follows:
the invention discloses a preparation method of a carbon nano tube, which comprises the steps of firstly obtaining a cleaned metal substrate, placing the cleaned substrate on a clamping sheet, and loading the substrate into a reaction furnace of chemical vapor deposition equipment in a vertical posture; then injecting protective gas into the reaction furnace at a certain speed, heating to 200 ℃ at a certain heating rate, and keeping for 20 minutes; the substrate is placed in the center of the furnace to ensure that the substrate can be stabilized at the temperature for the growth of the carbon nano tube; firstly, introducing protective gas to sweep so as to clean the atmosphere in the furnace and eliminate the adverse effect of other gases on the growth of the carbon nano tube, thereby ensuring the stability of a system in the furnace and being more beneficial to the subsequent growth of the carbon nano tube; the temperature was raised to 200 c at a steady rate and held for 20 minutes to allow the gas to be distributed relatively quickly and uniformly within the furnace. Because the growth of the carbon nano tube is sensitive to the change of conditions, in order to avoid poor growth effect of the carbon nano tube caused by the influence of the environment in the furnace, under the condition that the introducing speed of the protective gas is not changed, the temperature is increased to 700-900 ℃, the mixed solution is injected at a stable speed to grow the carbon nano tube, so that the gas flow rate in the furnace and the injection speed of the mixed carbon source solution are kept stable, and the carbon nano tube is stably transited to the growth stage of the carbon nano tube.
According to the technical scheme, compared with the prior art, the method for preparing the carbon nano tube by hydrogen-free chemical vapor deposition has the following excellent effects:
according to the preparation method of the carbon nano tube, the growth of the carbon nano tube is regulated and controlled by adding the alcohol organic matter into the carbon source solution, so that the prepared carbon nano tube has high purity and good structural integrity, the preparation of the carbon nano tube is realized under the condition of no hydrogen atmosphere, the problems of safety risk, tail gas treatment and high cost in the prior art can be solved, and the preparation method is suitable for market popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an electron scan of carbon nanotubes prepared in example 1 of the present invention.
FIG. 2 is a high-resolution TEM image of the carbon nanotubes prepared in example 1 of the present invention.
Fig. 3 is a raman spectrum of the carbon nanotube prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely in the following description with reference to the embodiments of the present invention and the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preferred embodiment of this patent provides a method for preparing carbon nanotubes by hydrogen-free chemical vapor deposition, comprising the steps of:
s1, obtaining a cleaned metal substrate, placing the cleaned metal substrate on a clamp so that the cleaned metal substrate is loaded into a reaction furnace of chemical vapor deposition equipment in a vertical posture, wherein the volume of the reaction furnace is 5L;
s2, preparing a carbon source solution containing a catalyst and an alcohol organic matter with a regulating and controlling function, and transferring the solution into liquid injection equipment;
s3, injecting protective gas into the reaction furnace at a certain speed, heating to 200 ℃ at a certain heating rate, and keeping the temperature for 20 minutes;
and S4, under the condition that the injection rate of the protective gas is not changed, heating to 700-900 ℃ at a fixed rate, and injecting a mixed solution of a carbon source solution and an alcohol organic matter to grow the carbon nano tube to obtain the carbon nano tube.
Specifically, in step S1, the substrate subjected to the cleaning process is obtained, and the substrate subjected to the cleaning process is placed on the chuck so as to be loaded into the reaction furnace of the chemical vapor deposition apparatus in a vertical posture. In the embodiment of the invention, the carbon nano tube is prepared on the substrate by a chemical vapor deposition method.
In a further embodiment, the metal substrate is selected from two-dimensional or three-dimensional structural metals with a melting point of more than 800 ℃, such as at least one of nickel flake/nickel foam, copper flake/copper foam, tungsten flake/tungsten foam, and titanium flake/titanium foam. The foam nickel substrate adopted by the embodiment has large surface area, can be uniformly attached with the metal catalyst, does not influence the catalytic performance of the catalyst at high temperature, and is beneficial to uniform, stable and ordered growth of the carbon nano tube.
In a further embodiment, the alcohol organic is at least one selected from methanol, ethanol, propanol and ethylene glycol. In this embodiment, a certain volume fraction of alcohol organic compound is added to the carbon source solution, so as to replace hydrogen. Preparing alcohol organic matters in a carbon source solution and ferrocene into a mixed solution; when the mixed solution is injected, the alcohol organic matter is gasified and thermally decomposed at high temperature to generate hydrogen; the growth of the carbon nano tube is promoted under the condition of not introducing external hydrogen. In addition, hydrogen generated by the high-temperature decomposition of the alcohol organic matter can directly promote the generation of the metal catalyst and regulate and control the growth of the carbon nano tube.
In a further embodiment, the protective gas is at least one selected from nitrogen, argon, helium, and the like. At least one of nitrogen, argon and helium adopted in the embodiment can ensure the stability of the catalyst and is beneficial to the growth of the carbon nano tube.
Specifically, in step S2, a carbon source solution containing a catalyst and an organic alcohol that plays a role in regulation is prepared, and the solution is transferred to a syringe and loaded on a syringe pump.
In a further embodiment, the alcohol organic is at least one selected from methanol, ethanol, propanol and ethylene glycol; in the embodiment of the invention, the alcohol organic matter is pyrolyzed at high temperature under the drive of the carrier gas to generate hydrogen; the generated hydrogen promotes the generation of metal catalyst, inhibits the generation of amorphous carbon in the growth process of the carbon nano tube and enables the carbon nano tube to grow better; the carbon nano tube can grow under the condition of not introducing hydrogen; the safety of the carbon nano tube preparation process is improved, and the cost is reduced.
In a further embodiment, the catalyst is metal catalyst particles having a particle size of nanometer size. The catalyst of the embodiment of the invention is generated from ferrocene. Ferrocene sublimes above 200 ℃ to produce small-sized iron metal catalyst particles; the metal catalyst particles are attached to the surface of the substrate under the drive of the protective gas along with the carbon source solution, carbon atoms formed by gasifying and cracking the carbon source solution at high temperature are dissolved on the surfaces of the metal catalyst particles immediately, and after the carbon source solution reaches a saturated state, the carbon atoms are separated out from the surfaces of the catalyst particles to form an ordered carbon nano tube structure, so that the growth of the carbon nano tube is realized.
Specifically, in step S3, a protective gas is injected into the reaction furnace at a certain rate, and the temperature is raised to 200 ℃ at a certain rate and maintained for 20 minutes; in order to ensure that the carbon nano tube has a better growth environment in preparation and growth, the protective gas is firstly introduced for purging to ensure that the atmosphere in the furnace is clean, and the adverse effect of other gases on the growth of the carbon nano tube is eliminated, so that the stability of the system in the furnace is ensured, and the subsequent growth of the carbon nano tube is facilitated.
In a further embodiment, the mixed carbon source solution is injected at a rate of 0.005ml/min to 0.500ml/min. The speed can lead the carbon source solution, the ferrocene and the alcohol organic matters to be cracked into reactants for the growth of the carbon nano tube at a stable speed.
In a further embodiment, the flow rate of the injected protective gas is 100sccm to 3000sccm. The flow velocity can stabilize the environment in the furnace, and is beneficial to the gasification of the subsequent carbon source solution after entering; the carbon source solution can be rapidly diffused in the furnace along with the carrier gas, so that the catalyst is more uniformly attached to the substrate.
Specifically, in step S4, under the condition that the injection rate of the protective gas is not changed, the temperature is raised to 700 to 900 ℃ at a fixed rate, and a mixed solution of a carbon source solution and an alcohol organic substance is injected to perform growth of the carbon nanotube, so as to obtain the carbon nanotube. When the protective gas and the carbon source solution are injected at a stable rate, the chemical reaction balance in the furnace can be ensured, the growth condition of the carbon nano tube is met, the cracking rate of the carbon source, the decomposition rate of the alcohol organic matter and the generation rate of the metal catalyst reach a dynamic balance, and the growth of the carbon nano tube is facilitated.
In a further embodiment, the step of growing the carbon nanotubes by using the mixed carbon source solution comprises: injecting mixed carbon source solution to grow carbon nanotube in 10-180 min. In the embodiment of the invention, the growth of the carbon nano tube can be carried out by injecting the mixed carbon source solution, wherein the carbon source solution provides carbon atoms through pyrolysis, ferrocene sublimes to provide metal catalyst particles, and alcohol organic matters are decomposed to generate hydrogen; the invention realizes the preparation method of growing the carbon nano tube without introducing hydrogen through the idea of producing hydrogen by decomposing alcohols at high temperature.
In a further embodiment, the invention prepares a mixed solution of 5-50% volume fraction of alcohol organic matter and carbon source solution and introduces the mixed solution into a reaction furnace for the growth of the carbon nano tube, and the volume fraction can make the hydrogen quantity of alcohol decomposition and the carbon atom precipitation rate reach dynamic balance; the problem that the carbon nano tube cannot grow due to the insufficient hydrogen yield caused by too low volume fraction is avoided; meanwhile, the inhibition effect on the growth of the carbon nano tube caused by excessive hydrogen generated due to overhigh volume fraction is avoided.
The above technical solution is illustrated by a plurality of examples below.
Example 1
A method for preparing carbon nanotubes by hydrogen-free chemical vapor deposition, comprising the following steps:
1) Obtaining a cleaned foamed nickel substrate, wherein the shape of the foamed nickel substrate is square; the dimensions of the foamed nickel substrate were 5cm x 5cm.
2) Placing the foam nickel base plate on a clamping piece, and placing the foam nickel base plate into a tube furnace in a vertical posture; wherein the tube furnace has a tube diameter of 8cm, a length of 100cm and a volume of about 5L.
3) Preparing a mixed carbon source solution; dichlorobenzene, ferrocene and ethanol with 10 percent volume fraction are selected to prepare a mixed carbon source solution, and the mixed carbon source solution is loaded on a syringe pump.
4) Introducing argon gas into the tube furnace, and heating the tube furnace to 200 ℃ at the speed of 10 ℃/min; the flow rate of argon is 500sccm, and is kept for 20 minutes; and the tube furnace was heated to a specified temperature of 745 ℃.
5) The flow rate of argon gas is increased to 1000sccm, and the prepared mixed carbon source solution is injected at the same time, wherein the injection rate is 0.13ml/min. The carbon nanotube growth was started with a growth time of 40 minutes.
6) And stopping injecting the mixed carbon source solution and heating after the carbon nano tubes finish growing, keeping injecting argon, and taking out the substrate with the carbon nano tubes after the temperature of the tubular furnace is reduced to be below 100 ℃.
FIG. 1 is a scanning electron micrograph of carbon nanotubes prepared according to example 1 above. A relatively complete and clear carbon nanotube structure can be observed from fig. 1; and the carbon nano tube presents a net structure; carbon nanotubes are fine and long.
Fig. 2 is a high resolution transmission electron microscope image of the carbon nanotubes prepared from example 1 above. The internal structure of the carbon nanotubes can be further observed from fig. 2; and the tube wall structure of the carbon nano tube is clear. And from figure 2 some amorphous carbon on the tube wall can be observed, presumably due to thermal decomposition of ethanol.
Fig. 3 is a raman spectrum of the carbon nanotube prepared in the above example 1. The peak D is 1350cm -1 About, G peak at 1580cm -1 Left and right. I is D /I G The peak intensity ratio of (a) may reflect the degree of graphitization of the carbon, as well as the degree of defects in the carbon. 2D peak at 2700cm -1 And the stacking mode of the graphene can be represented. From figure I D /I G The ratio of the peak heights of (a) can be concluded that the sample prepared in example 1 has a high degree of graphitization and relatively few defects; while the structure of multilayer graphene is present in the sample.
Example 2
A method for preparing carbon nano-tubes by hydrogen-free chemical vapor deposition comprises the following steps:
1) Obtaining a cleaned foamy copper substrate, wherein the shape of the foamy copper substrate is square; the foam copper substrate size is 5cm x 5cm.
2) Placing the foamy copper substrate on a clamping piece, and placing the foamy copper substrate into a tube furnace in a vertical posture; wherein, the tube furnace has a tube diameter of 8cm, a length of 100cm and a volume of about 5L.
3) Preparing a mixed carbon source solution; pyridine, ferrocene and 15% volume fraction propanol were selected to prepare a mixed carbon source solution and loaded onto a syringe pump.
4) Introducing argon gas into the tube furnace, and heating the tube furnace to 200 ℃ at the speed of 10 ℃/min; the flow rate of argon is 500sccm, and is kept for 20 minutes; and the tube furnace was heated to a specified temperature of 760 ℃.
5) The flow rate of argon gas is increased to 1000sccm, and the prepared mixed carbon source solution is injected at the same time, wherein the injection rate is 0.13ml/min. The carbon nanotube growth was started with a growth time of 20 minutes.
6) And stopping injecting the mixed carbon source solution and stopping heating after the growth of the carbon nano tubes is finished, keeping injecting argon, and taking out the substrate with the carbon nano tubes after the temperature of the tubular furnace is reduced to be below 100 ℃.
Example 3
A method for preparing carbon nanotubes by hydrogen-free chemical vapor deposition, comprising the following steps:
1) Obtaining a cleaned titanium foam sheet substrate, wherein the shape of the substrate is square; the foamed titanium substrate size was 5cm x 5cm.
2) Placing the titanium foam substrate on a clamping sheet, and placing the titanium foam substrate into a tube furnace in a vertical posture; wherein the tube furnace has a tube diameter of 8cm, a length of 100cm and a volume of about 5L.
3) Preparing a mixed carbon source solution; a mixed carbon source solution was prepared from xylene, ferrocene and 15% volume fraction methanol and loaded onto a syringe pump.
4) Introducing nitrogen gas into the tube furnace, and heating the tube furnace to 200 ℃ at the speed of 10 ℃/min; the flow rate of nitrogen is 500sccm, and the temperature is kept for 20 minutes; and the tube furnace was heated to a specified temperature of 745 ℃.
5) The flow rate of argon gas is increased to 1000sccm, and the prepared mixed carbon source solution is injected at the same time, wherein the injection rate is 0.26ml/min. The carbon nanotube growth was started with a growth time of 10 minutes.
6) And stopping injecting the mixed carbon source solution and stopping heating after the growth of the carbon nano tubes is finished, keeping injecting argon, and taking out the substrate with the carbon nano tubes after the temperature of the tubular furnace is reduced to be below 100 ℃.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A method for preparing carbon nanotubes by hydrogen-free chemical vapor deposition is characterized by comprising the following steps:
1) Placing the cleaned metal substrate on a clamping sheet, and loading the metal substrate into a reaction furnace of chemical vapor deposition equipment in a vertical posture;
2) Preparing a mixed solution containing a catalyst, an alcohol organic matter and a carbon source, and transferring the mixed solution into controllable liquid injection equipment;
3) Injecting protective gas into the reaction furnace in the step 1), and then heating to 200 ℃ for 20 minutes;
4) Under the condition that the injection rate of the protective gas is not changed, continuously heating the reaction furnace, and injecting the mixed solution prepared in the step 2) to grow the carbon nano tube;
5) And stopping injecting the mixed solution after the growth of the carbon nano tube is finished, stopping heating the reaction furnace, and taking out the substrate with the carbon nano tube after the temperature in the furnace is naturally reduced to be below 100 ℃, thus finishing the preparation of the carbon nano tube by hydrogen-free chemical vapor deposition.
2. The method of claim 1, wherein the metal substrate is selected from two-dimensional or three-dimensional structural metals with a melting point of more than 800 ℃, and is at least one of nickel flake/nickel foam, copper flake/copper foam, tungsten flake/tungsten foam, and titanium flake/titanium foam.
3. The method of claim 1, wherein the alcohol organic is at least one selected from methanol, ethanol, propanol and ethylene glycol;
the carbon source is organic hydrocarbon and is at least one selected from benzene, pyridine, xylene and dichlorobenzene;
the catalyst is nano-sized metal catalyst particles, and the catalyst is ferrocene.
4. The method of claim 1 or 3, wherein the volume fraction of the alcoholic organic substance is 5-50%, and the injection rate of the mixed solution is 0.005-0.500 ml/min.
5. The method of claim 1, wherein the protective gas is at least one selected from the group consisting of nitrogen, argon and helium, and the protective gas is injected at a flow rate of 100sccm to 3000sccm.
6. The method for preparing carbon nanotubes by hydrogen-free chemical vapor deposition as claimed in claim 1, wherein the temperature in step 4) is raised to 700 ℃ to 900 ℃ at a rate of 10 to 40 ℃/min.
7. The method of claim 1, wherein the step 5) of injecting the mixed solution for carbon nanotube growth is performed for 10 to 180 minutes.
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