CN107539972B - Preparation method of metal oxide nanotube and metal oxide nanotube - Google Patents
Preparation method of metal oxide nanotube and metal oxide nanotube Download PDFInfo
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Abstract
The invention provides a preparation method of a metal oxide nanotube and the metal oxide nanotube, and the method comprises the following steps: setting a slit on a substrate; heating the substrate to 900-1005 ℃ by taking metal nano particles as a catalyst, and controlling a mixed gas consisting of a carbon source gas, hydrogen and water vapor to flow through the heated substrate so as to grow a 1-10 cm carbon nano tube in the middle of the slit on the substrate; preheating the carbon nano tube at 250-350 ℃; under the protection of the atmosphere of gas which does not participate in the reaction, metal oxide is deposited on the surface of the preheated carbon nano tube to form at least one layer of metal oxide film; the carbon nano tube and at least one layer of metal oxide film deposited on the surface of the carbon nano tube form the metal oxide nano tube. The method can prepare centimeter-sized oxide nanotubes, greatly improve the length of the oxide nanotubes and reduce the structural defects of the oxide nanotubes.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of a metal oxide nanotube and the metal oxide nanotube.
Background
Metal oxide nanotubes have been used in a variety of fields, such as biosensors and dye-sensitized solar cells, based on their unique one-dimensional hollow structure. The length of the metal oxide nanotubes has a significant impact on their precise control in various applications.
At present, the main preparation method of the metal oxide nanotube is an anodic oxidation method, for example, a titanium oxide nanotube array is prepared by the anodic oxidation method. In the preparation process, titanium and titanium dioxide are dissolved mainly under the action of an electric field, so that titanium metal at the anode is self-organized to form an ordered porous structure, namely a titanium oxide nanotube array.
The preparation process of the anodic oxidation method is uncontrollable, and the length of the metal oxide nanotube prepared by the method is small and generally limited to be less than micrometers.
Disclosure of Invention
The embodiment of the invention provides a preparation method of a metal oxide nanotube and the metal oxide nanotube, which can improve the length of the metal oxide nanotube.
The embodiment of the invention provides a preparation method of a metal oxide nanotube, which comprises the following steps:
setting a slit on a substrate;
heating the substrate to 900-1005 ℃ by taking metal nano particles as a catalyst, and controlling a mixed gas consisting of a carbon source gas, hydrogen and water vapor to flow through the heated substrate so as to grow a 1-10 cm carbon nano tube in the middle of the slit on the substrate;
preheating the carbon nano tube at 250-350 ℃;
under the protection of the atmosphere of gas which does not participate in the reaction, metal oxide is deposited on the surface of the preheated carbon nano tube to form at least one layer of metal oxide film;
the carbon nano tube and at least one layer of metal oxide film deposited on the surface of the carbon nano tube form the metal oxide nano tube.
In the method for preparing the metal oxide nanotube, the centimeter-sized ultra-long carbon nanotube is prepared by a chemical vapor deposition method, and then the metal oxide film is deposited on the surface of the prepared ultra-long carbon nanotube, so that the metal oxide film wraps the whole carbon nanotube to form the centimeter-sized metal oxide nanotube, and the length of the oxide nanotube is greatly improved. Due to the increase of the length of the oxide nanotube, the prepared oxide nanotube can be used for fine application scenes of electronics, micro-nano machines and the like.
And in the preparation process, the carbon nano tube is preheated at 250-350 ℃ to remove gas and other impurities adsorbed on the carbon nano tube, so that when metal oxide is deposited on the surface of the carbon nano tube, the formed metal oxide film is regular and has fewer structural defects.
The substrate for growing the carbon nanotubes is generally a silicon substrate, and the process of arranging the slits on the substrate can be realized by the following method:
a certain number of slits are carved on the substrate by utilizing a photoetching method, or a plurality of substrates with smaller sizes are adhered on the surface of a substrate with larger size, and then the slits among the substrates with smaller sizes are the slits.
In addition, the metal nanoparticles may be any one of Fe, Mo, Cu, and Cr nanoparticles.
The preparation process of the metal nanoparticles can be as follows: coating ethanol solution or water solution of metal chloride of any one of Fe, Mo, Cu and Cr on a substrate, then placing the substrate in a reactor, heating the reactor to 800-1000 ℃, and then introducing hydrogen or mixed gas of hydrogen and inert gas into the reactor for reduction reaction to prepare the metal nano-particles.
Because the preparation technology of the carbon nano tube is developed completely, the operation process for preparing the metal oxide nano tube based on the carbon nano tube is very simple, the conditions are suitable, and the growth speed of the metal oxide on the surface of the carbon nano tube is higher, so that the metal oxide nano tube is favorable for producing the metal oxide nano tube in batch quickly.
Optionally, after growing the carbon nanotube in the middle of the slit on the substrate, before the preheating the carbon nanotube, the method further includes:
placing a solid metal oxide and the carbon nano tubes in the same segmented temperature-controlled reactor, wherein the solid metal oxide is placed in a first heating area of the segmented temperature-controlled reactor, and the carbon nano tubes are placed in a second heating area of the segmented temperature-controlled reactor;
the preheating the carbon nanotube comprises: and controlling the temperature of the second heating area to be 250-350 ℃.
Optionally, the metal oxide is deposited on the surface of the carbon nanotube after preheating, and the method includes:
controlling the temperature of the first heating area to be 500-800 ℃, sublimating the solid metal oxide into gaseous metal oxide, and conveying the gaseous metal oxide in the first heating area to the second heating area by using the gas which does not participate in the reaction;
and controlling the temperature of the second heating area to be 450-750 ℃, further heating the preheated carbon nano tube, and keeping the gaseous metal oxide in contact with the carbon nano tube for 10-30 min.
Optionally, the controlling the temperature of the second heating zone to be 450 ℃ to 750 ℃ includes: and controlling the temperature of the second heating area to be 500-700 ℃.
The deposition of the metal oxide on the surface of the carbon nano tube is controlled in a segmented temperature control reactor (a tubular furnace with a segmented temperature control function and the like), so that the segmented temperature control of the solid metal oxide and the carbon nano tube is facilitated, and the operation is convenient. After the solid metal oxide is sublimated into the gaseous metal oxide in the first heating area, the gaseous metal oxide is conveyed to the second heating area by utilizing gas which does not participate in the reaction, and meanwhile, the temperature of the second heating area is increased, and is slightly higher than that of the first heating area, so that the gaseous metal oxide with higher temperature from the first heating area can be deposited on the carbon nano tube more easily. Because the deposition process is carried out under the protection of the atmosphere of gas which does not participate in the reaction, the concentration of the gaseous metal oxide is lower, so that the metal oxide is easier to deposit on the carbon nano tube as a metal oxide film instead of a crystal. In addition, the contact time of the carbon nano tube and the gaseous metal oxide is controlled to be less than 30min, so that the phenomenon that the metal oxide is deposited on the carbon nano tube to form a two-dimensional layered crystal structure due to overlong time is avoided.
Optionally, the gas not participating in the reaction comprises: the flow rate of argon or mixed gas of argon and hydrogen is 20 ml/min-100 ml/min, and when the gas not participating in the reaction is the mixed gas of argon and hydrogen, the volume part ratio of the hydrogen to the argon is 0.05-1.
Controlling the flow rate of the gas not participating in the reaction can control the concentration of the gaseous metal oxide, thereby being beneficial to the generation of the metal oxide film. The mixed gas of hydrogen and argon is used as the gas which does not participate in the reaction, and the hydrogen can react with part of oxygen remained in the reactor, so that the damage of the oxygen to the structure of the carbon nano tube at high temperature is avoided, and the structural integrity of the metal oxide nano tube is further improved.
Optionally, the metal oxide comprises: any one of molybdenum oxide, zinc oxide, or tungsten oxide.
In this embodiment, the sublimation temperature of the selected metal oxide is low, for example, the sublimation temperature of molybdenum oxide is about 500 ℃, the sublimation temperature of zinc oxide is about 800 ℃, and the sublimation temperature of tungsten oxide is about 700 ℃, which facilitates the vaporization of the metal oxide. Furthermore, the layer material such as molybdenum oxide has high rigidity and high bending energy, and is difficult to form an ultrafine nanotube structure with a diameter of about 10 nm. The surface energy can be reduced by utilizing the adsorption property of the surface of the carbon nano tube, and the formation of the metal oxide nano tube is assisted.
Meanwhile, molybdenum oxide, zinc oxide and tungsten oxide all have good surface properties, and molybdenum oxide is an n-type semiconductor for example, and oxygen vacancies and heteroatoms on the surface of the molybdenum oxide can adsorb oxygen species in the air, so that the electrophilicity of the surface can be improved. And the increase of the surface energy level can trap electrons in a semiconductor conduction band, namely, the electrical property of the material can be changed. Meanwhile, it can adsorb other gases, thereby adjusting the electrical property. Through the test of the electrical property, the component in the gas environment can be sensed. After the metal oxide nanotube structure is formed, the specific surface area can be greatly increased, and is higher than that of a two-dimensional crystal structure of molybdenum oxide, so that the adsorption performance of the material is enhanced. Molybdenum oxide nanotubes to trace amounts of NO2、CO、CH4The gases have good sensitivity and selectivity. Therefore, the molybdenum oxide nanotube is a gas sensitive material with great potential.
In addition, the metal oxide nanotube film can be formed by preparing the molybdenum oxide nanotube with a carbon nanotube array with a larger density or directly doping and compounding the carbon nanotube structure in the molybdenum oxide film. The formed molybdenum oxide nanotube film can be used as a hole transport layer of a solar cell, and the transport performance of the transport layer can be improved due to the nanostructure of the molybdenum oxide nanotube film.
The embodiment of the invention also provides a metal oxide nanotube, which comprises: carbon nanotubes and at least one layer of metal oxide film; wherein the content of the first and second substances,
the at least one layer of metal oxide film is deposited on the surface of the carbon nano tube;
the length of the carbon nano tube is 1 cm-10 cm.
Optionally, the diameter of the carbon nanotube is 1nm to 4 nm.
Optionally, the thickness of each metal oxide thin film is 0.5nm to 1.3 nm.
Optionally, the composition of the metal oxide thin film comprises: any one of molybdenum oxide, zinc oxide, or tungsten oxide.
Optionally, the diameter of the metal oxide nanotube is 2nm to 15 nm;
optionally, the metal oxide nanotubes have a lattice orientation; wherein the [001] crystal orientation of the crystal lattice in the metal oxide thin film is the same as the axial direction of the carbon nanotube, that is, the [001] crystal orientation of the crystal lattice is always along the axial direction of the carbon nanotube.
The embodiment of the invention provides a preparation method of a metal oxide nanotube and the metal oxide nanotube, wherein a centimeter-level ultra-long carbon nanotube is prepared in a chemical vapor deposition mode, and then a metal oxide film is deposited on the surface of the prepared ultra-long carbon nanotube, so that the metal oxide film wraps the whole carbon nanotube to form the centimeter-level metal oxide nanotube, and the length of the oxide nanotube is greatly improved.
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 introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a projection electron microscope image of a metal oxide nanotube according to an embodiment of the present invention;
FIG. 2 is an atomic force microscope image of a metal oxide nanotube according to an embodiment of the present invention;
FIG. 3 is an atomic force microscope image of another metal oxide nanotube provided by an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention, and based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts belong to the scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. In the following examples, various devices, reagents and materials used are generally commercially available unless otherwise specified.
The invention is further illustrated by the following specific examples.
The process of preparing carbon nanotubes mainly comprises the following steps:
etching a plurality of slits on the substrate by a photoetching method or a pasting method;
coating an ethanol solution or an aqueous solution of any one of metal chlorides of Fe, Mo, Cu and Cr on a substrate, then placing the substrate in a reactor, heating the reactor to 800-1000 ℃, and then introducing hydrogen or a mixed gas of hydrogen and an inert gas into the reactor for a reduction reaction to prepare metal nanoparticles;
the metal nano-particles are used as a catalyst, the substrate is heated to 900-1005 ℃ through a reactor, and the mixed gas consisting of carbon source gas, hydrogen and water vapor is controlled to flow through the substrate, so that the carbon nano-tube with the length of 1-10 cm grows in the middle of the slit on the substrate.
The process for preparing the metal oxide nanotube mainly comprises the following steps:
placing a solid metal oxide and the carbon nano tubes in the same segmented temperature-controlled reactor, wherein the solid metal oxide is placed in a first heating area of the segmented temperature-controlled reactor, and the carbon nano tubes are placed in a second heating area of the segmented temperature-controlled reactor;
controlling the temperature of the second heating area to be 250-350 ℃ so as to preheat the carbon nano tube;
controlling the temperature of the first heating area to be 500-800 ℃, sublimating the solid metal oxide into gaseous metal oxide, and conveying the gaseous metal oxide in the first heating area to the second heating area by using the gas which does not participate in the reaction;
controlling the temperature of the second heating area to be 450-750 ℃, further heating the preheated carbon nano tube, and keeping the gaseous metal oxide in contact with the carbon nano tube for 1-30 min so as to deposit the metal oxide on the surface of the carbon nano tube to form at least one layer of metal oxide film;
the carbon nano tube and at least one layer of metal oxide film deposited on the surface of the carbon nano tube form the metal oxide nano tube.
The process of preparing carbon nanotubes and the process of preparing metal oxide nanotubes are described in detail in the following examples.
Example 1 is intended to illustrate the preparation of carbon nanotubes using metallic iron nanoparticles as a catalyst and the preparation of molybdenum oxide nanotubes using the prepared carbon nanotubes and molybdenum oxide powder.
Example 1:
step A1: utilizing a photoetching method to arrange a millimeter-scale slit on a substrate;
step B1: coating an ethanol solution of ferric trichloride with the concentration of 0.02mol/L on a substrate, feeding the substrate coated with the ethanol solution of ferric trichloride into a quartz tube reactor, introducing a mixed gas of hydrogen and argon into the quartz tube reactor, heating the quartz tube reactor, and controlling the flow rate of the hydrogen to be 200ml/min and the flow rate of the argon to be 400 ml/min; when the temperature is increased to 900 ℃, carrying out reduction reaction for 20min at constant temperature to obtain the metallic iron nano-particles with the particle size;
step C1: heating the temperature of the quartz tube reactor to 1005 ℃, closing argon gas at the moment, changing the flow rate of hydrogen gas to 70ml/min, simultaneously introducing 20ml/min of mixed gas of methane and water vapor, and reacting for 50min to obtain a10 cm carbon nano tube;
step D1: and C1, placing the molybdenum oxide powder and the carbon nano tubes prepared in the step C1 into a sectional temperature-controlled tube furnace, wherein the substrate loaded with the carbon nano tubes is placed at the downstream of the tube furnace, and the molybdenum oxide powder is placed at the upstream of the tube furnace.
Step E1: the temperature downstream of the tube furnace was adjusted to 300 c to preheat the carbon nanotubes and remove adsorbed gases and other impurities from the carbon nanotubes.
Step F1: regulating the temperature of the upstream of the tube furnace to 500 ℃, sublimating the molybdenum oxide powder into gaseous molybdenum oxide, introducing mixed gas flow of 20ml/min hydrogen and argon, and conveying the sublimed gaseous molybdenum oxide to the downstream of the tube furnace, namely a heating region of the carbon nano tube, by using the mixed gas flow of the hydrogen and the argon.
Step G1: the temperature of the downstream of the tube furnace is adjusted to 450 ℃, the carbon nano tube is further heated, so that the gaseous molybdenum oxide contacts the carbon nano tube with slightly lower temperature, and the temperature is kept for 10 min. So that the molybdenum oxide forms a single-layer or multi-layer molybdenum oxide film on the surface of the carbon nano tube, namely a single-wall or multi-wall molybdenum oxide nano tube structure.
The SEM image of the generated molybdenum oxide nanotube is shown in FIG. 1, and it can be seen from the chart that the molybdenum oxide nanotube has obvious warp orientation, and the [001] crystal direction of the crystal lattice is always along the axial direction of the carbon nanotube, which shows that the method is a novel method for preparing the nanotube with specific crystal lattice orientation. Further, as a result of measuring the diameter of the molybdenum oxide nanotube by an atomic force microscope, as shown in fig. 2 and 3, a maximum of 4 molybdenum oxide thin films were observed, each of which had a thickness of 1.3nm, a diameter of the molybdenum oxide nanotube of 2nm to 15nm, and a diameter of the inner carbon nanotube of 1nm to 4 nm.
Example 2:
the reaction process was similar to example 1 except that the temperature downstream of the tube furnace was adjusted to 250 ℃ while preheating the carbon nanotubes.
Example 3:
the reaction process was similar to example 1 except that the flow rate of the mixed gas stream of hydrogen and argon was adjusted to 100 ml/min.
Example 4:
the reaction process was similar to example 1 except that the temperature downstream of the tube furnace was adjusted to 400 ℃ as the carbon nanotubes were further heated.
Example 5:
the reaction process was similar to example 1 except that the carbon nanotubes were kept in an atmosphere of gaseous molybdenum oxide and argon for 12 min.
Example 6 is intended to illustrate the preparation of carbon nanotubes using metallic copper nanoparticles as a catalyst, and the preparation of zinc oxide nanotubes using the prepared carbon nanotubes and zinc oxide powder.
Example 6:
step A6: using a pasting method to set a millimeter-scale slit on the substrate;
step B6: coating an ethanol solution of copper chloride with the concentration of 0.5mol/L on a substrate, sending the substrate coated with the ethanol solution of copper chloride into a quartz tube reactor, introducing a mixed gas of hydrogen and argon into the quartz tube reactor, heating the quartz tube reactor, and controlling the flow rate of the hydrogen to be 200ml/min and the flow rate of the argon to be 500 ml/min; when the temperature is raised to 950 ℃, carrying out reduction reaction for 30min at constant temperature to obtain metal copper nanoparticles;
step C6: heating the quartz tube reactor to 1005 ℃, closing argon gas, changing the flow rate of hydrogen gas to 160ml/min, introducing a mixed gas of methane and water vapor at 80ml/min, and reacting for 120min to obtain a 1cm carbon nano tube;
step D6: and C6, placing the zinc oxide powder and the carbon nanotubes prepared in the step C6 in a sectional temperature-controlled tube furnace, wherein the substrate loaded with the carbon nanotubes is placed downstream of the tube furnace and the zinc oxide powder is placed upstream of the tube furnace.
Step E6: the temperature downstream of the tube furnace was adjusted to 250 c to preheat the carbon nanotubes and remove adsorbed gases and other impurities from the carbon nanotubes.
Step F6: regulating the temperature at the upstream of the tube furnace to 800 ℃, sublimating the zinc oxide powder into gaseous zinc oxide, simultaneously introducing a mixed gas flow of 100ml/min hydrogen and argon, and conveying the sublimed gaseous zinc oxide to the downstream of the tube furnace, namely a heating region of the carbon nano tube, by using the mixed gas flow of the hydrogen and the argon.
Step G6: the temperature of the downstream of the tube furnace was adjusted to 750 ℃, and the carbon nanotubes were further heated to bring the gaseous zinc oxide into contact with the slightly lower temperature carbon nanotubes and held for 10 min. So that the zinc oxide forms a single-layer or multi-layer zinc oxide film on the surface of the carbon nano tube, namely a single-wall or multi-wall zinc oxide nano tube structure.
Example 7:
the reaction process was similar to example 6 except that the flow rate of the mixed gas stream of hydrogen and argon was adjusted to 40ml/min and the carbon nanotubes were maintained in an atmosphere of hydrogen and argon and gaseous zinc oxide for 14 min.
Example 8:
the reaction process was similar to example 6 except that the temperature downstream of the tube furnace was adjusted to 700 c as the carbon nanotubes were further heated.
Example 9:
the reaction procedure is similar to that of example 6, except that the temperature upstream of the tube furnace is adjusted to 850 ℃ in order that the zinc oxide powder sublimes into gaseous zinc oxide.
Example 10 is intended to illustrate the preparation of tungsten oxide nanotubes using the carbon nanotubes and tungsten oxide powder prepared in example 1.
Example 10:
the process of preparing the carbon nanotubes in steps a10 to C10 is the same as the process of steps a1 to C1 in example 1, and is not repeated herein;
step D10: and C1, placing the tungsten oxide powder and the carbon nano tubes prepared in the step C1 into a sectional temperature-controlled tube furnace, wherein the substrate loaded with the carbon nano tubes is placed at the downstream of the tube furnace, and the tungsten oxide powder is placed at the upstream of the tube furnace.
Step E10: the temperature downstream of the tube furnace was adjusted to 350 c to preheat the carbon nanotubes and remove adsorbed gases and other impurities from the carbon nanotubes.
Step F10: regulating the temperature of the upstream of the tube furnace to 700 ℃, sublimating the tungsten oxide powder into gaseous tungsten oxide, simultaneously introducing 50ml/min argon, and conveying the sublimed gaseous tungsten oxide to the downstream of the tube furnace by utilizing argon airflow, namely a heating area of the carbon nano tube.
Step G10: the temperature of the downstream of the tube furnace was adjusted to 600 ℃, and the carbon nanotubes were further heated to bring the gaseous tungsten oxide into contact with the slightly lower temperature carbon nanotubes and held for 15 min. So that the tungsten oxide forms a single-layer or multi-layer tungsten oxide film on the surface of the carbon nano tube, namely a single-wall or multi-wall tungsten oxide nano tube structure.
Example 11:
the reaction process was similar to example 10 except that the flow rate of argon was adjusted to 70ml/min and the carbon nanotubes were kept in an atmosphere of argon and gaseous tungsten oxide for 25 min.
Example 12:
the reaction process was similar to example 10 except that the temperature downstream of the tube furnace was adjusted to 650 ℃ as the carbon nanotubes were further heated.
According to the scheme, the embodiments of the invention have at least the following beneficial effects:
1. in the embodiment of the invention, the centimeter-level ultra-long carbon nano tube is prepared by a chemical vapor deposition method, and then the metal oxide film is deposited on the surface of the prepared ultra-long carbon nano tube, so that the metal oxide film wraps the whole carbon nano tube to form the centimeter-level metal oxide nano tube, and the length of the oxide nano tube is greatly improved. Due to the increase of the length of the oxide nanotube, the prepared oxide nanotube can be used for fine application scenes of electronics, micro-nano machines and the like.
2. In the embodiment of the invention, the carbon nano tube is preheated to remove gas and other impurities adsorbed on the carbon nano tube, so that when metal oxide is deposited on the surface of the carbon nano tube, the formed metal oxide film is more regular, and the existing structural defects are fewer.
3. In the embodiment of the invention, as the preparation technology of the carbon nano tube is developed completely, the operation process of preparing the metal oxide nano tube based on the carbon nano tube is very simple, the conditions are suitable, and the growth speed of the metal oxide on the surface of the carbon nano tube is higher, so that the metal oxide nano tube is favorable for producing the metal oxide nano tube in batch.
4. In the embodiment of the invention, the metal oxide is controlled to be deposited on the surface of the carbon nano tube in the segmented temperature control reactor, so that the segmented temperature control of the solid metal oxide and the carbon nano tube is facilitated, and the operation process for preparing the metal oxide nano tube is simpler.
5. In the embodiment of the invention, the metal oxide with good surface performance is adopted to prepare the oxide nanotube, so that the electrical performance of the material can be changed, and the electrical performance can also be adjusted. After the metal oxide nanotube structure is formed, the specific surface area can be greatly increased, and the adsorption performance of the material is enhanced, so that the metal oxide nanotube can be used as a gas-sensitive material to detect trace gas.
6. In the embodiment of the invention, the surface energy can be reduced by utilizing the adsorption performance of the surface of the carbon nano tube, thereby being beneficial to assisting metal oxide or other rigid two-dimensional materials to form the nano tube.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a" does not exclude the presence of other similar elements in a process, method, article, or apparatus that comprises the element.
Finally, it is to be noted that: the above description is only a preferred embodiment of the present invention, and is only used to illustrate the technical solutions of the present invention, and not to limit the protection scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (8)
1. A method for preparing metal oxide nanotubes, comprising:
setting a slit on a substrate;
heating the substrate to 900-1005 ℃ by taking metal nano particles as a catalyst, and controlling a mixed gas consisting of a carbon source gas, hydrogen and water vapor to flow through the heated substrate so as to grow a 1-10 cm carbon nano tube in the middle of the slit on the substrate;
preheating the carbon nano tube at 250-350 ℃;
under the protection of the atmosphere of gas which does not participate in the reaction, metal oxide is deposited on the surface of the preheated carbon nano tube to form at least one layer of metal oxide film;
the carbon nano tube and at least one layer of metal oxide film deposited on the surface of the carbon nano tube form the metal oxide nano tube;
after growing the carbon nanotube in the middle of the slit on the substrate, before preheating the carbon nanotube, further comprising:
placing a solid metal oxide and the carbon nano tubes in the same segmented temperature-controlled reactor, wherein the solid metal oxide is placed in a first heating area of the segmented temperature-controlled reactor, and the carbon nano tubes are placed in a second heating area of the segmented temperature-controlled reactor;
the preheating the carbon nanotube comprises: controlling the temperature of the second heating area to be 250-350 ℃;
the metal oxide is deposited on the surface of the preheated carbon nanotube and comprises:
controlling the temperature of the first heating area to be 500-800 ℃, sublimating the solid metal oxide into gaseous metal oxide, and conveying the gaseous metal oxide in the first heating area to the second heating area by using the gas which does not participate in the reaction;
controlling the temperature of the second heating area to be 450-750 ℃, further heating the preheated carbon nano tube, and keeping the gaseous metal oxide in contact with the carbon nano tube for 10-30 min;
wherein the flow rate of the gas not participating in the reaction is 20 ml/min-100 ml/min.
2. The production method according to claim 1,
the temperature of the second heating area is controlled to be 450-750 ℃, and the method comprises the following steps: and controlling the temperature of the second heating area to be 500-700 ℃.
3. The production method according to claim 1,
the metal oxide includes: any one of molybdenum oxide, zinc oxide, or tungsten oxide.
4. The method according to any one of claims 1 to 3,
the gas not participating in the reaction includes: the flow rate of argon or mixed gas of argon and hydrogen is 20 ml/min-100 ml/min, and when the gas not participating in the reaction is the mixed gas of argon and hydrogen, the volume part ratio of the hydrogen to the argon is 0.05-1.
5. A metal oxide nanotube prepared by the method of any one of claims 1 to 4, comprising: carbon nanotubes and at least one layer of metal oxide film; wherein the content of the first and second substances,
the at least one layer of metal oxide film is deposited on the surface of the carbon nano tube;
the length of the carbon nano tube is 1 cm-10 cm.
6. The metal oxide nanotubes of claim 5,
the thickness of each layer of the metal oxide film is 0.5 nm-1.3 nm.
7. The metal oxide nanotubes of claim 5,
the composition of the metal oxide thin film comprises: any one of molybdenum oxide, zinc oxide, or tungsten oxide.
8. The metal oxide nanotubes of any one of claims 5 to 7,
the diameter of the metal oxide nanotube is 2 nm-15 nm;
and/or the presence of a gas in the gas,
the diameter of the carbon nano tube is 1 nm-4 nm;
and/or the presence of a gas in the gas,
the metal oxide nanotubes have a lattice orientation; wherein the content of the first and second substances,
the [001] crystal orientation of the crystal lattice in the metal oxide thin film is the same as the axial direction of the carbon nanotube.
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| CN106990266B (en) * | 2017-04-26 | 2019-06-11 | 清华大学 | It is a kind of to prepare needle point, the method for probe and needle point, probe |
| CN107101760B (en) * | 2017-04-26 | 2019-10-11 | 清华大学 | A kind of preparation method of precise torsion balance, precise torsion balance and application method |
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