CN109201068B - Preparation method and application of catalyst for synthesizing carbon nanocoil with reduced byproduct carbon layer - Google Patents
Preparation method and application of catalyst for synthesizing carbon nanocoil with reduced byproduct carbon layer Download PDFInfo
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Abstract
A preparation method and application of a catalyst for synthesizing a carbon nano coil with a reduced byproduct carbon layer belong to the technical field of material preparation. Soluble ferric salt and soluble tin salt are used as raw materials, and the weight ratio of Fe: dissolving Sn in a reducing solvent according to a molar ratio of 60: 1-3: 1, preparing Fe-Sn-O catalyst particles by adopting a solvothermal method, and synthesizing the high-purity carbon nanocoil with few or even no byproduct carbon layer by utilizing the prepared catalyst by adopting a thermal CVD method. The preparation method provided by the invention has the advantages of simple process and low cost, can be used for synthesizing the high-purity carbon nanocoil without the byproduct carbon layer, and has a prominent application prospect.
Description
Technical Field
The invention belongs to the technical field of material preparation, and relates to a preparation method and application of a catalyst for reducing synthesis of a byproduct carbon layer carbon nanocoil.
Background
Due to the unique three-dimensional spiral nano structure, the carbon nano coil has excellent electromagnetic property, mechanical property and dispersion property, and can be widely applied to occasions such as electromagnetic wave-absorbing materials, strain sensing devices, micro-nano electromechanical systems, three-dimensional nano spiral templates and the like. At present, there are many methods for preparing carbon nanocoils disclosed, and the most suitable method for industrial production is Chemical Vapor Deposition (CVD), in which a catalyst is supported on the surface of a substrate and placed in a CVD system, and a carbon source gas is allowed to flow over the surface of the catalyst under certain reaction conditions to cause catalytic decomposition and deposition. In the process of synthesizing the carbon nano coil by using the method, the selection of the high-efficiency catalyst is very critical, and the morphology, the components and the particle size of the catalyst influence the synthesis quality of the carbon nano coil.
The catalysts suitable for the growth of carbon nanocoils disclosed so far mainly comprise iron, cobalt, nickel, tungsten transition metals and their alloys, especially catalysts represented by iron-tin oxide alloy (Fe-Sn-O) particles are widely proven to be capable of synthesizing carbon nanocoils at high efficiency and low cost. The presently disclosed methods for preparing Fe-Sn-O catalysts mainly include solution methods (publication: d.w.li et al, Advanced Materials Research, vols.60-61, pp.251-,255,2009), sol-gel methods (publication: d.w.li et al, Carbon,48(1), 170:. 175, 2010.), ion sputtering methods (publication: Fu, Xin, et al, Carbon 99(2016):43-48, 2016), all of which can successfully prepare Fe-Sn-O catalysts for synthesizing Carbon nanocoils, but they have a common problem that an amorphous Carbon layer with a thickness of several micrometers to tens of micrometers is grown at the bottom of the synthesized Carbon nanocoil during the synthesis of the Carbon nanocoil, so that the purity of the synthesized Carbon nanocoil is greatly reduced, and the application thereof is severely limited on a large scale; the main reason for this phenomenon is that all of the catalysts used are not suitable for synthesizing carbon nanocoils, and some catalysts can only synthesize amorphous carbon layers, so that the overall purity of the prepared carbon nanocoils is significantly reduced, and the problem of purification is additionally introduced. Therefore, the preparation of highly efficient uniform catalysts for synthesizing carbon nanocoils without byproduct carbon layers is receiving increasing attention from many researchers.
Disclosure of Invention
The invention aims to provide a catalyst for reducing synthesis of a carbon nano coil with a byproduct carbon layer, a preparation method and application thereof, aiming at the problems of the amorphous carbon layer as a byproduct and low purity of the carbon nano coil in the synthesis process of the carbon nano coil in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a catalyst for synthesizing a carbon nanocoil with a reduced by-product carbon layer, comprising the steps of:
(a) with soluble Fe3+Or Fe2+Salt and soluble Sn4+Or Sn2+Salt is taken as a raw material, and the weight ratio of Fe: dissolving Sn atoms in a molar ratio of 60: 1-3: 1 in a reducing solvent, uniformly mixing to obtain a catalyst precursor solution, and adding Fe in the catalyst precursor solution3+Or Fe2+The concentration of (B) is in the range of 0.01 to 0.05 mol/l.
(b) And (b) transferring the catalyst precursor solution prepared in the step (a) to a high-temperature reaction kettle, controlling the reaction temperature to be 160-220 ℃ in a solvothermal system, naturally cooling to room temperature after carrying out solvothermal reaction in the high-pressure kettle for 5-30 hours, filtering, washing and drying the obtained red precipitate to obtain single red Fe-Sn-O catalyst powder, wherein the particle size is distributed between 100nm and 500 nm.
The Fe: the molar ratio of Sn atoms is preferably 10: 1.
The reducing solvent includes N, N-Dimethylformamide (DMF), acetonitrile, ethylene glycol, isopropanol, etc., preferably DMF.
Said soluble Fe3+Or Fe2+Salts include, but are not limited to, ferric (nitrite) nitrate, ferric (nitrite) chloride, -, ferric sulfate, soluble Sn4+Or Sn2+Salts include, but are not limited to, tin (ene) oxide, tin (ene) chloride, and Fe3+Or Fe2+Salt with Sn4+Or Sn2+The salts may be combined in any combination.
The application of the catalyst for synthesizing the carbon nanocoil with less by-product carbon layer and even no by-product carbon layer by using the catalyst comprises the following steps:
dispersing the prepared catalyst powder into water or an organic solution at room temperature to obtain a catalyst dispersion liquid, wherein the concentration of the catalyst is 0.5-5 mg/ml; the catalyst dispersion is attached to the surface of the substrate and then dried, or the catalyst powder is directly attached to the surface of the substrate or attached to the surface of the substrate by surface modification. Putting the substrate carrying the catalyst into a CVD system, and reacting for 3-300 min at the reaction temperature of 650-800 ℃ by taking acetylene as a carbon source and argon, nitrogen or other inert gases as protective gases; the carbon nano coil with little or no byproduct carbon layer is obtained by growth.
The substrate comprises quartz, silicon and SiO2Graphene, stainless steel, metal oxides, borides, nitrides, fibers, ceramics, and the like, including flat plates and spheres, in various shapes.
In the CVD system, the flow rate of the carbon source is 15sccm, and the flow rate of the protective gas is 245 sccm.
Compared with the prior art, the invention has the beneficial effects that: the catalyst for synthesizing the carbon nano coil with few or even no byproduct carbon layers is prepared by a one-step solvothermal method, and the preparation method is simple, easy to operate, simple in process and low in cost; the carbon nano coil synthesized by the catalyst prepared by the method has the characteristics of high purity, less or even no byproduct carbon layer, is beneficial to large-scale industrial preparation, and has outstanding application prospect.
Drawings
FIG. 1 is an EDS elemental analysis test spectrum of the catalyst powder prepared in example 1.
FIG. 2 is an X-ray diffraction pattern (XRD) of the catalyst powder prepared in example 1.
FIG. 3 is an X-ray photoelectron spectroscopy analysis chart (Sn element portion) of the catalyst powder prepared in example 1.
FIG. 4 is a Scanning Electron Micrograph (SEM) of a catalyst powder prepared in example 1.
Fig. 5 is a top Scanning Electron Micrograph (SEM) of the carbon nanocoil prepared in example 1.
Fig. 6 is a Scanning Electron Microscope (SEM) cross-sectional view of the carbon nanocoil prepared in example 1.
Fig. 7 is an EDS elemental analysis test spectrum of the catalyst powder prepared in example 2.
Fig. 8 is a Scanning Electron Microscope (SEM) cross-sectional view of the carbon nanocoil prepared in example 2.
Fig. 9 is a Scanning Electron Microscope (SEM) cross-sectional view of the carbon nanocoil prepared in example 3.
FIG. 10 is a Scanning Electron Microscope (SEM) cross-sectional view of the carbon nanocoil prepared in example 4.
Detailed Description
The invention is best described below with reference to the accompanying drawings.
The catalyst for preparing the carbon nanocoil with reduced product byproduct carbon layer according to the embodiment of the present invention is mainly composed of iron oxide (α -Fe)2O3) And tin oxide (SnO)2) Aggregate particle composition.
Example 1:
(1) catalyst for producing carbon nanocoils with reduced byproduct carbon layer
Mixing 404mg Fe (NO)3)3·9H2O and 35.06mg SnCl4·5H2Dissolving O (the molar ratio of Fe to Sn is 10:1) in 36ml of N, N-Dimethylformamide (DMF), carrying out ultrasonic treatment until the mixed solution is completely dissolved, transferring the mixed solution after uniform mixing and dispersion into a high-temperature high-pressure reaction kettle, controlling the reaction temperature at 180 ℃ in a solvothermal system, reacting for 30 hours, naturally cooling to room temperature, filtering the obtained red precipitate, washing, and drying to obtain single red powder.
FIG. 1 shows the EDS elemental analysis test results of the catalyst powder, which shows that the red powder mainly consists of three elements, Fe, Sn and O; FIG. 2 is an X-ray diffraction pattern (XRD) of the catalyst powder, which is seen with alpha-Fe2O3The peak positions of the standard map PDF #33-0664 are consistent, which indicates that the Fe element in the catalyst is from alpha-Fe2O3Since the crystallinity of the oxide of Sn element in the product is not good, the X-ray diffraction pattern cannot determine its specific valence state, and further test confirmation is required. FIG. 3 is an X-ray photoelectron spectroscopy (XPS) chart of the catalyst powder, in which Sn 3d can be seen5/2And Sn 3d3/2The peak of the binding energy appears at 486.2eV and 494.6eV, which can be confirmed from the XPS standard binding energy comparison table2The oxidation states of the Sn element and the Sn element are consistent, so that the Sn element in the catalyst is determined to be from SnO2. FIG. 4 is a Scanning Electron Micrograph (SEM) of the catalyst powder prepared, showing that the powder is a loose and porous aggregate structure, which is advantageous for the catalyst to carbon in the next reaction processThe adsorption of source gas, the distribution range of catalyst particles is 100nm-500 nm.
(2) Carbon nanocoil with little or no byproduct carbon layer prepared by using catalyst
Accurately weighing the catalyst powder prepared in the step (1), dispersing the catalyst powder into alcohol with the concentration of 0.5mg/ml, taking a reaction supporting substrate silicon wafer, respectively washing the reaction supporting substrate silicon wafer with acetone, alcohol and deionized water, and drying the reaction supporting substrate silicon wafer for later use. Measuring 1ml of catalyst dispersion liquid drop and coating the catalyst dispersion liquid drop on the surface of a substrate; after drying, the catalyst-loaded substrate was placed in a CVD system with acetylene (C)2H2) The carbon source is used, the flow rate is 15sccm, argon (Ar) is used as protective gas, the flow rate is 245sccm, the reaction temperature is 700 ℃, the reaction time is 30min, and the temperature is naturally reduced after the reaction is finished.
Fig. 5 is a top Scanning Electron Microscope (SEM) of a typical product after reaction, which shows that a large amount of carbon nanocoils are synthesized with a purity of over 95%. FIG. 6 is a scanning electron microscope image of a cross-section of a typical reaction product, and it can be seen from the image that most of the contact surfaces of the bottom of the product and the substrate are carbon nanocoils and carbon nanofibers, and no dense and thick amorphous carbon layer is generated, so that the purity of the carbon nanocoils in the reaction product is greatly improved.
Example 2:
(1) a catalyst for producing a carbon nanocoil with reduced by-product carbon layer.
273mg of FeCl3·6H2O and 35.06mg SnCl4·5H2Adding 36ml of acetonitrile into O (the molar ratio of Fe to Sn is 10:1), carrying out ultrasonic treatment until the mixed solution is completely dissolved, transferring the mixed solution after uniform mixing and dispersion into a high-temperature high-pressure reaction kettle, controlling the reaction temperature at 220 ℃ in a solvothermal system, carrying out reaction for 5 hours, naturally cooling to room temperature, filtering the obtained red precipitate, washing and drying to obtain single red powder.
FIG. 7 is an EDS elemental analysis test pattern of the catalyst powder prepared in example 2, and the test results show that the red powder is mainly composed of three elements of Fe, Sn and O, and the peak where Si is simultaneously present is from the substrate silicon wafer.
(2) Carbon nanocoil with little or no byproduct carbon layer prepared by using catalyst
Accurately weighing a certain amount of the catalyst powder prepared in the step (1), dispersing the catalyst powder into alcohol for ultrasonic standby application, wherein the concentration is 1mg/ml, and cleaning a reaction-supported substrate quartz plate with acetone, alcohol and deionized water respectively and then drying the quartz plate for standby application. Measuring 1ml of catalyst dispersion liquid and coating the catalyst dispersion liquid on the surface of a substrate; after drying, the catalyst-loaded substrate was placed in a CVD system with acetylene (C)2H2) The carbon source is used, the flow rate is 15sccm, argon (Ar) is used as protective gas, the flow rate is 245sccm, the reaction temperature is 650 ℃, and the reaction time is 120 min. And naturally cooling after the reaction is finished. FIG. 8 is a scanning electron microscope image of a cross-section of a typical reaction product, and it can be seen from the image that most of the contact surfaces of the bottom of the product and the substrate are carbon nanocoils and carbon nanofibers, and no dense and thick amorphous carbon layer is generated.
Example 3:
(1) a catalyst for producing carbon nanocoils with reduced by-product carbon layers.
200mg of Fe2(SO4)3·9H2O and 35.06mg SnCl2·2H2Dissolving O (Fe: Sn atom molar ratio is 10:1) in 36ml of isopropanol, carrying out ultrasonic treatment until the mixed solution is completely dissolved, transferring the mixed solution after uniform mixing and dispersion to a high-temperature high-pressure reaction kettle, controlling the reaction temperature at 160 ℃ in a solvothermal system, reacting for 20 hours, naturally cooling to room temperature, filtering, washing and drying the obtained red precipitate to obtain single red powder.
(2) Carbon nanocoil with little or no byproduct carbon layer prepared by using catalyst
Accurately weighing a certain amount of the catalyst powder prepared in the step (1), dispersing the catalyst powder into water or an organic solution for standby application by ultrasonic treatment, wherein the concentration of the catalyst powder is 1mg/ml, and cleaning a reaction-supported substrate graphite substrate by acetone, alcohol and deionized water respectively and then drying the reaction-supported substrate graphite substrate for standby application. Measuring 1ml of catalyst dispersion liquid and coating the catalyst dispersion liquid on the surface of a substrate quartz plate; after drying, the catalyst-loaded substrate was placed in a CVD system with acetylene (C)2H2) The carbon source is used, the flow rate is 15sccm, argon (Ar) is used as protective gas, the flow rate is 240sccm, the reaction temperature is 710 ℃, and the reaction time is 90 min. After the reaction is finished, the reaction is naturalAnd (5) cooling.
FIG. 9 is a scanning electron microscope image of a cross-section of a typical reaction product, and it can be seen from the image that most of the contact surfaces of the bottom of the product and the substrate are carbon nanocoils and carbon nanofibers, and no dense and thick amorphous carbon layer is generated.
Example 4:
(1) a catalyst for producing a carbon nanocoil with reduced by-product carbon layer.
287mg of Fe (NO)3)2·6H2O and 35.06mg SnCl4·5H2Dissolving O (Fe: Sn atom molar ratio is 10:1) in 36ml of ethylene glycol, carrying out ultrasonic treatment until the mixed solution is completely dissolved, transferring the mixed solution after uniform mixing and dispersion to a high-temperature high-pressure reaction kettle, controlling the reaction temperature at 200 ℃ in a solvothermal system, reacting for 30 hours, naturally cooling to room temperature, filtering, washing and drying the obtained red precipitate to obtain single red powder.
(2) Carbon nanocoil with little or no byproduct carbon layer prepared by using catalyst
Accurately weighing a certain amount of the catalyst powder prepared in the step (1), dispersing the catalyst powder into water or an organic solution, and performing ultrasonic treatment for standby application, wherein the concentration is as follows: 5mg/ml, and respectively cleaning the reaction supported stainless steel substrate with acetone, alcohol and deionized water, and drying for later use. Measuring 1ml of catalyst dispersion liquid and coating the catalyst dispersion liquid on the surface of a substrate; after drying, the catalyst-loaded substrate was placed in a CVD system with acetylene (C)2H2) As a carbon source, at a flow rate of 15sccm, nitrogen (N)2) The flow rate is 240sccm for the protective gas, the reaction temperature is 710 ℃, and the reaction time is 30 min. And naturally cooling after the reaction is finished. FIG. 10 is a scanning electron microscope image of a cross-section of a typical reaction product, and it can be seen from the image that most of the contact surfaces of the bottom of the product and the substrate are carbon nanocoils and carbon nanofibers, and no dense and thick amorphous carbon layer is generated.
Example 5:
(1) a catalyst for producing a carbon nanocoil with reduced by-product carbon layer.
Mixing 404mg Fe (NO)3)3·9H2O and 35.06mg SnCl4·5H2O (Fe: Sn atomic mol)Dissolving the mixed solution into 36ml of ethylene glycol according to a molar ratio of 10:1), performing ultrasonic treatment until the mixed solution is completely dissolved, transferring the mixed solution after uniform mixing and dispersion into a high-temperature high-pressure reaction kettle, controlling the reaction temperature to be 200 ℃ in a solvothermal system, performing reaction for 30 hours, naturally cooling to room temperature, filtering the obtained red precipitate, washing and drying to obtain single red powder.
(2) Carbon nanocoil with little or no byproduct carbon layer prepared by using catalyst
Accurately weighing a certain amount of the catalyst powder prepared in the step (1), dispersing the catalyst powder into water or an organic solution for standby (the concentration is 1mg/ml) by ultrasound, taking a reaction supporting substrate silicon wafer, respectively washing the reaction supporting substrate silicon wafer by acetone, alcohol and deionized water, and drying the reaction supporting substrate silicon wafer for standby. Measuring 1ml of catalyst dispersion liquid and coating the catalyst dispersion liquid on the surface of a substrate; after drying, the catalyst-loaded substrate was placed in a CVD system with acetylene (C)2H2) As a carbon source, at a flow rate of 15sccm, nitrogen (N)2) The flow rate is 240sccm for the protective gas, the reaction temperature is 710 ℃, and the reaction time is 30 min. And naturally cooling after the reaction is finished. The product is the carbon nano coil with little or no byproduct carbon layer.
Example 6:
(1) a catalyst for producing a carbon nanocoil with reduced by-product carbon layer.
198mgFeCl2·4H2O and 35.06mg SnCl4·5H2Dissolving O (Fe: Sn atom molar ratio is 10:1) in 36ml of isopropanol, carrying out ultrasonic treatment until the mixed solution is completely dissolved, transferring the mixed solution after uniform mixing and dispersion to a high-temperature high-pressure reaction kettle, controlling the reaction temperature at 220 ℃ in a solvothermal system, reacting for 30 hours, naturally cooling to room temperature, filtering, washing and drying the obtained red precipitate to obtain single red powder.
(2) Carbon nanocoil with little or no by-product carbon layer prepared by using the catalyst
Accurately weighing a certain amount of the catalyst powder prepared in the step (1), dispersing the catalyst powder into water or an organic solution for standby by ultrasonic treatment, wherein the concentration of the catalyst powder is 3mg/ml, taking a reaction supporting substrate ceramic substrate, respectively cleaning the reaction supporting substrate ceramic substrate by acetone, alcohol and deionized water, and drying the reaction supporting substrate ceramic substrate for standby. Measuring 1mlCoating the catalyst dispersion liquid on the surface of the substrate; after drying, the catalyst-loaded substrate was placed in a CVD system with acetylene (C)2H2) The carbon source is used, the flow rate is 15sccm, argon (Ar) is used as protective gas, the flow rate is 240sccm, the reaction temperature is 710 ℃, and the reaction time is 30 min. And naturally cooling after the reaction is finished. The product is the carbon nano coil without the byproduct carbon layer.
Example 7:
(1) a catalyst for producing a carbon nanocoil with reduced by-product carbon layer.
Mixing 404mg Fe (NO)3)3·9H2O and 105.18mg SnCl4·5H2Dissolving O (Fe: Sn atom molar ratio is 3:1) in 100ml of N, N-Dimethylformamide (DMF), carrying out ultrasonic treatment until the mixed solution is completely dissolved, transferring the mixed solution after uniform mixing and dispersion to a high-temperature high-pressure reaction kettle, controlling the reaction temperature at 180 ℃ in a solvothermal system, reacting for 5 hours, naturally cooling to room temperature, filtering the obtained red precipitate, washing and drying to obtain single red powder.
(2) Carbon nanocoil with little or no byproduct carbon layer prepared by using catalyst
Accurately weighing a certain amount of the catalyst powder prepared in the step (1), dispersing the catalyst powder into water or an organic solution for standby ultrasonic treatment (the concentration is 5mg/ml), and taking a reaction supporting substrate SiO2Respectively cleaning with acetone, alcohol and deionized water, and drying. Measuring 1ml of catalyst dispersion liquid and coating the catalyst dispersion liquid on the surface of a substrate; after drying, the catalyst-loaded substrate was placed in a CVD system with acetylene (C)2H2) The carbon source is used, the flow rate is 15sccm, argon (Ar) is used as protective gas, the flow rate is 240sccm, the reaction temperature is 650 ℃, and the reaction time is 120 min. And naturally cooling after the reaction is finished. The product is the carbon nano coil with little or no byproduct carbon layer.
Example 8:
(1) a catalyst for producing a carbon nanocoil with reduced by-product carbon layer.
Mixing 404mg Fe (NO)3)3·9H2O and 5.26mg SnCl4·5H2O (Fe: Sn atomic molar ratio of 60: 1)) Dissolving the red precipitate in 10ml of N, N-Dimethylformamide (DMF), performing ultrasonic treatment until the mixed solution is completely dissolved, transferring the mixed solution after uniform mixing and dispersion to a high-temperature high-pressure reaction kettle, controlling the reaction temperature at 180 ℃ in a solvothermal system, reacting for 15 hours, naturally cooling to room temperature, filtering the obtained red precipitate, washing and drying to obtain single red powder.
(2) Carbon nanocoil with little or no byproduct carbon layer prepared by using catalyst
Accurately weighing a certain amount of the catalyst powder prepared in the step (1), dispersing the catalyst powder into water or an organic solution for standby (the concentration is 2mg/ml), taking a reaction supporting substrate silicon wafer, respectively washing the reaction supporting substrate silicon wafer with acetone, alcohol and deionized water, and drying the reaction supporting substrate silicon wafer for standby. Measuring 1ml of catalyst dispersion liquid and coating the catalyst dispersion liquid on the surface of a substrate graphite substrate; after drying, the catalyst-loaded substrate was placed in a CVD system with acetylene (C)2H2) The carbon source is used, the flow rate is 15sccm, argon (Ar) is used as protective gas, the flow rate is 240sccm, the reaction temperature is 800 ℃, and the reaction time is 10 min. And naturally cooling after the reaction is finished. The product is the carbon nano coil with little or no byproduct carbon layer.
Example 9:
(1) a catalyst for producing a carbon nanocoil with reduced by-product carbon layer.
278mg of FeSO4·7H2O and 22.56mg SnCl2·2H2Dissolving O (Fe: Sn atom molar ratio is 10:1) in 36ml of N, N-Dimethylformamide (DMF), carrying out ultrasonic treatment until the mixed solution is completely dissolved, transferring the mixed solution after uniform mixing and dispersion to a high-temperature high-pressure reaction kettle, controlling the reaction temperature at 180 ℃ in a solvothermal system, reacting for 30 hours, naturally cooling to room temperature, filtering the obtained red precipitate, washing and drying to obtain single red powder.
(2) Carbon nanocoil with little or no byproduct carbon layer prepared by using catalyst
Accurately weighing a certain amount of the catalyst powder prepared in the step (1), dispersing the catalyst powder into water or an organic solution for standby ultrasonic treatment (the concentration is 2mg/ml), taking the reaction supporting substrate alumina pellets, and respectively using acetone, alcohol and deionized waterAnd (5) cleaning with water and drying for later use. Measuring 1ml of catalyst dispersion liquid and coating the catalyst dispersion liquid on the surface of a substrate graphite substrate; after drying, the catalyst-loaded substrate was placed in a CVD system with acetylene (C)2H2) The carbon source is used, the flow rate is 15sccm, argon (Ar) is used as protective gas, the flow rate is 240sccm, the reaction temperature is 800 ℃, and the reaction time is 10 min. And naturally cooling after the reaction is finished. The product is the carbon nano coil with little or no byproduct carbon layer.
Example 10:
(1) a catalyst for producing a carbon nanocoil with reduced by-product carbon layer.
287mg of Fe (NO)3)2·6H2O and 22.56mg SnCl2·2H2Dissolving O (Fe: Sn atom molar ratio is 10:1) in 36ml of acetonitrile, carrying out ultrasonic treatment until the mixed solution is completely dissolved, transferring the mixed solution after uniform mixing and dispersion to a high-temperature high-pressure reaction kettle, controlling the reaction temperature at 180 ℃ in a solvothermal system, reacting for 30 hours, naturally cooling to room temperature, filtering, washing and drying the obtained red precipitate to obtain single red powder.
(2) Carbon nanocoil with little or no byproduct carbon layer prepared by using catalyst
Accurately weighing a certain amount of the catalyst powder prepared in the step (1), dispersing the catalyst powder into water or an organic solution for standby (the concentration is 2mg/ml), taking a reaction supporting substrate silicon wafer, respectively washing the reaction supporting substrate silicon wafer with acetone, alcohol and deionized water, and drying the reaction supporting substrate silicon wafer for standby. Measuring 1ml of catalyst dispersion liquid and coating the catalyst dispersion liquid on the surface of a substrate graphite substrate; after drying, the catalyst-loaded substrate was placed in a CVD system with acetylene (C)2H2) The carbon source is used, the flow rate is 15sccm, argon (Ar) is used as protective gas, the flow rate is 240sccm, the reaction temperature is 800 ℃, and the reaction time is 10 min. And naturally cooling after the reaction is finished. The product is the carbon nano coil with little or no byproduct carbon layer.
The above examples demonstrate that: the Fe-Sn-O catalyst particles designed and synthesized by the technical scheme provided by the invention can be used for efficiently preparing the carbon nano coil with few or even no byproduct amorphous carbon layers by using a simple CVD method, and the synthetic purity of the carbon nano coil is obviously improved.
While the foregoing examples have been described in order to facilitate a person of ordinary skill in the art to understand and practice the present invention. The embodiments described above only represent embodiments of the present invention, but it should not be understood that the scope of the present invention is limited thereby, and it should be noted that those skilled in the art can make various changes and modifications without departing from the spirit of the present invention, which falls into the protection scope of the present invention.
Claims (7)
1. Use of a catalyst for carbon nanocoil synthesis with reduced by-product carbon layer, characterized in that the catalyst is prepared by the steps of:
(a) with soluble Fe3+Or Fe2+Salt and soluble Sn4+Or Sn2+Salt is taken as a raw material, and the weight ratio of Fe: dissolving Sn atoms in a molar ratio of 60: 1-3: 1 in a reducing solvent, uniformly mixing to obtain a catalyst precursor solution, and adding Fe in the catalyst precursor solution3+Or Fe2+The concentration range of (A) is 0.01-0.05 mol/l;
(b) transferring the catalyst precursor solution prepared in the step (a) to a high-temperature reaction kettle, controlling the reaction temperature to be 160-220 ℃ in a solvothermal system, naturally cooling to room temperature after carrying out solvothermal reaction in the high-pressure kettle for 5-30 hours, filtering, washing and drying the obtained red precipitate to obtain single red Fe-Sn-O catalyst powder, wherein the particle size is distributed between 100nm and 500 nm;
the catalyst obtained by the preparation method is used for synthesizing the carbon nanocoil with little or even no byproduct carbon layer, and comprises the following steps:
dispersing the prepared catalyst powder into water or an organic solution at room temperature to obtain a catalyst dispersion liquid, wherein the concentration of the catalyst is 0.5-5 mg/ml; attaching the catalyst dispersion to the surface of a substrate and then drying, or directly attaching the catalyst powder to the surface of the substrate or attaching the catalyst powder to the surface of the substrate through surface modification; and placing the substrate carrying the catalyst into a CVD system, reacting for 3-300 min at the reaction temperature of 650-800 ℃ by taking acetylene as a carbon source and inert gas as protective gas, and growing to obtain the carbon nanocoil with little or even no byproduct carbon layer.
2. Use of a catalyst for carbon nanocoil synthesis with reduced by-product carbon layer as claimed in claim 1, wherein the Fe: the molar ratio of Sn atoms is 10: 1.
3. Use of the catalyst for carbon nanocoil synthesis with reduced by-product carbon layer according to claim 1 or 2, wherein said soluble Fe is3+Or Fe2+Salts include ferric nitrate/ferrous nitrate, ferric chloride/ferrous chloride, ferric sulfate; the soluble Sn4+Or Sn2+Salts include stannic/stannous chloride.
4. The use of the catalyst for carbon nanocoil synthesis with reduced byproduct carbon layer according to claim 1 or 2, wherein the reducing solvent comprises N, N-dimethylformamide, acetonitrile, ethylene glycol, isopropanol.
5. The use of the catalyst for carbon nanocoil synthesis with reduced byproduct carbon layer according to claim 3, wherein the reducing solvent comprises N, N-dimethylformamide, acetonitrile, ethylene glycol, isopropanol.
6. The use of a catalyst for carbon nanocoil synthesis with reduced byproduct carbon layer as claimed in claim 1 wherein said substrate comprises quartz, silicon, SiO2Graphite, graphene, stainless steel, metal oxides, borides, nitrides, fibers, ceramics, including flat and spherical shaped solid substrates.
7. The use of the catalyst for carbon nanocoil synthesis with reduced byproduct carbon layer as claimed in claim 1 or 6, wherein the flow rate of the carbon source is 15sccm and the flow rate of the shielding gas is 245sccm in the CVD system.
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| CN109761218A (en) * | 2019-03-26 | 2019-05-17 | 大连领峰高科新技术发展有限公司 | A method of for continuous production helical form carbon material fluidized bed and utilize its continuous production helical form carbon material |
| CN109761220A (en) * | 2019-03-26 | 2019-05-17 | 大连领峰高科新技术发展有限公司 | A kind of method of fluidized bed process continuous production helical form carbon material |
| CN110639532A (en) * | 2019-09-23 | 2020-01-03 | 大连理工大学 | One-step hydrothermal synthesis method and application of catalyst for synthesizing high-purity carbon nanocoil |
| CN110642240B (en) * | 2019-09-23 | 2022-05-27 | 大连理工大学 | Method for synthesizing high-purity carbon nanocoil by using composite catalyst formed on basis of multiple small-size catalysts |
| CN111710991B (en) * | 2020-06-24 | 2021-08-10 | 大连理工大学 | Spiral carbon nano coil/core-shell structure magnetic nano particle composite material, preparation method and application thereof in electromagnetic wave field |
| CN114522242B (en) * | 2022-02-28 | 2023-02-03 | 深圳大学 | Magnetic drive spiral micro-nano motor and preparation method and application thereof |
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