CN107539972A - The preparation method and metal oxide nanotubes of a kind of metal oxide nanotubes - Google Patents

The preparation method and metal oxide nanotubes of a kind of metal oxide nanotubes Download PDF

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CN107539972A
CN107539972A CN201710771590.1A CN201710771590A CN107539972A CN 107539972 A CN107539972 A CN 107539972A CN 201710771590 A CN201710771590 A CN 201710771590A CN 107539972 A CN107539972 A CN 107539972A
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oxide
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CN107539972B (en
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魏飞
申博渊
谢欢欢
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Tsinghua University
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Tsinghua University
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Abstract

The invention provides a kind of preparation method of metal oxide nanotubes and metal oxide nanotubes, this method includes：Slit is set on substrate；Catalyst is made with metal nanoparticle, the substrate is heated to 900 DEG C~1005 DEG C, and control the mixed gas of carbon-source gas, hydrogen and vapor composition to flow through the substrate after heating, among the slit on the substrate, grow 1cm~10cm CNTs；At 250 DEG C~350 DEG C, the CNT is preheated；In the case where being not involved in the atmosphere protection of gas of reaction, metal oxide is deposited on the carbon nano tube surface after preheating, forms at least one layer of metal-oxide film；The CNT and at least one layer of metal-oxide film composition metal oxide nanotubes for being deposited on the carbon nano tube surface.This programme can prepare Centimeter Level oxide nano, greatly improve the length of oxide nano, and reduce the fault of construction of oxide nano.

Description

The preparation method and metal oxide nanotubes of a kind of metal oxide nanotubes
Technical field
The present invention relates to technical field of nano material, the preparation method of more particularly to a kind of metal oxide nanotubes and Metal oxide nanotubes.
Background technology
Based on its unique one-dimensional hollow structure, it is applied metal oxide nanotubes in multiple fields, such as Biology sensor and DSSC etc..The length of metal oxide nanotubes is to its in various applications accurate Control has material impact.
At present, the main preparation methods of metal oxide nanotubes are anodizing, for example, passing through anodic oxidation legal system Standby titania nanotube array.In preparation process, mainly dissolved by electric field action titanium and titanium dioxide, so that Self-organizing is carried out in the titanium of anode, forms ordered porous structural, i.e. titania nanotube array.
The preparation process of anodizing has uncontrollability, and the metal oxide nanotubes prepared by the method are grown Degree is smaller, is generally limited to below micron.
The content of the invention
The embodiments of the invention provide a kind of preparation method of metal oxide nanotubes and metal oxide nanotubes, The length of metal oxide nanotubes can be improved.
The embodiments of the invention provide a kind of preparation method of metal oxide nanotubes, including：
Slit is set on substrate；
Catalyst is made with metal nanoparticle, the substrate is heated to 900 DEG C~1005 DEG C, and control carbon-source gas, The mixed gas of hydrogen and vapor composition flows through the substrate after heating, among the slit on the substrate, Grow 1cm~10cm CNTs；
At 250 DEG C~350 DEG C, the CNT is preheated；
In the case where being not involved in the atmosphere protection of gas of reaction, metal oxide is deposited on the CNT after preheating Surface, form at least one layer of metal-oxide film；
The CNT is with being deposited on described at least one layer of metal-oxide film composition of the carbon nano tube surface Metal oxide nanotubes.
In the method for above-mentioned preparation metal oxide nanotubes, Centimeter Level is prepared by chemical vapor deposition manner first Overlength carbon nano pipe, then in the overlength carbon nano pipe surface depositing metal oxide film prepared so that metal aoxidize Thing film wraps up whole CNT, forms Centimeter Level metal oxide nanotubes, substantially increases the length of oxide nano Degree.Due to the increase of oxidate nano length of tube, the oxide nano prepared can be used for electronics and micro-nano mechanical etc. fine The application scenarios of change.
Also, in preparation process, pre-add heat treatment is carried out to CNT first at 250 DEG C~350 DEG C, removed with this Gas and the other impurities adsorbed on CNT are gone, so that when metal oxide is deposited on carbon nano tube surface, are formed Metal-oxide film it is more regular, existing fault of construction is less.
Wherein, the substrate for growing CNT is generally the substrate of silicon material, sets the process of slit can be with substrate It is accomplished by the following way：
A number of slit is carved in substrate using photoetching process, or is sticked in the larger substrate surface of a block size More less substrates of block size, then the gap between the less substrate of size is slit.
In addition, metal nanoparticle can be any one nano particle in Fe, Mo, Cu and Cr.
The preparation process of metal nanoparticle can be：By the second of the metal chloride of any one in Fe, Mo, Cu and Cr Alcoholic solution or the aqueous solution are applied in substrate, and then substrate is placed in reactor, and reactor is heated into 800 DEG C~1000 DEG C, the mixed gas that hydrogen or hydrogen and inert gas are then passed through into reactor carries out reduction reaction, and metal is made with this Nano particle.
Because the technology of preparing development of CNT is perfect, then the behaviour of metal oxide nanotubes is prepared based on CNT Make process very simple, and condition is suitable, and metal oxide is very fast in the speed of growth of carbon nano tube surface, therefore favorably Metal oxide nanotubes are produced in rapid batch metaplasia.
Alternatively, after the slit interstitial growth CNT on the substrate, described to described Before CNT is preheated, further comprise：
Solid metal oxide and the CNT are positioned in same sectional temperature-controlled reactor, wherein, it is described The first heating region that solid metal oxide is placed in the sectional temperature-controlled reactor, the CNT are placed in the segmentation Second heating region of temperature control reactor；
It is described that the CNT is preheated, including：Control the temperature of second heating region for 250 DEG C~ 350℃。
Alternatively, the metal oxide is deposited on the carbon nano tube surface after preheating, including：
The temperature for controlling first heating region is 500 DEG C~800 DEG C, and it is gas to make the solid metal oxide distillation State metal oxide, and the gas that reaction is not involved in described in utilization conveys the gaseous metal hydroxide of first heating region To second heating region；
The temperature for controlling second heating region is 450 DEG C~750 DEG C, further to the carbon nanometer after preheating Pipe is heated, and keeps the gaseous metal hydroxide to contact 10min~30min with the CNT.
Alternatively, the temperature for controlling second heating region is 450 DEG C~750 DEG C, including：Control described second The temperature of heating region is 500 DEG C~700 DEG C.
(having tube furnace of sectional temperature-controlled function etc.) in sectional temperature-controlled reactor, control metal oxide is deposited on carbon Nanotube surface, be advantageous to carry out solid metal oxide and CNT it is sectional temperature-controlled, it is easy to operation.When solid metallic oxygen Compound is aoxidized gaseous metal using the gas for being not involved in reaction after the distillation of the first heating region is gaseous metal hydroxide Thing is transmitted to the second heating region, while raises the temperature of the second heating region, this temperature compared with the first heating region temperature slightly Deng the gaseous metal hydroxide deposition for being more easy to make the temperature from the first heating region higher is on the carbon nanotubes.Due to deposition Process is carried out in the case where being not involved in the atmosphere protection of gas of reaction, and the concentration of gaseous metal hydroxide is relatively low, it is more easy in carbon Metal-oxide film is deposited as on nanotube, and it is noncrystal.In addition, contact of the control CNT with gaseous metal hydroxide Time is less than 30min, avoids overlong time, and metal oxide is deposited as two-dimensional layer crystal structure on the carbon nanotubes.
Alternatively, the gas for being not involved in reaction includes：The mixed gas of argon gas or argon gas and hydrogen, flow velocity are 20ml/min~100ml/min, when mixed gas of the gas for being not involved in reaction for argon gas and hydrogen, the hydrogen with The volume parts ratio of the argon gas is 0.05~1.
Control is not involved in the flow velocity of the gas of reaction, the concentration of gaseous metal hydroxide is can control, so as to be advantageous to metal The generation of sull.Using the mixed gas of hydrogen and argon gas as be not involved in reaction gas, hydrogen can with reactor The partial oxidation of remaining is reacted, so as to avoid at high temperature, structural damage of the oxygen to CNT, so as to further Improve the structural intergrity of metal oxide nanotubes.
Alternatively, the metal oxide includes：Any one in molybdenum oxide, zinc oxide or tungsten oxide.
In this embodiment, the sublimation temperature of the metal oxide of selection is relatively low, for example, the sublimation temperature of molybdenum oxide exists 500 DEG C or so, the sublimation temperature of zinc oxide is at 800 DEG C or so, and at 700 DEG C or so, this is easy to gold the sublimation temperature of tungsten oxide Category oxide is gasified.Also, the stratified material rigidity such as molybdenum oxide is stronger, and flexional is higher, it is difficult to forms diameter and exists 10nm or so superfine nano tubular construction.And the absorption property of carbon nano tube surface is utilized, surface energy can be reduced, assistant metal The formation of oxide nano, based on this, CNT template is equally applicable to prepare nanometer with other rigid two-dimensional materials Pipe.
Meanwhile molybdenum oxide, zinc oxide and tungsten oxide are respectively provided with good surface property, by taking molybdenum oxide as an example, it is a kind of n Type semiconductor, the oxygen species in air can be adsorbed due to the Lacking oxygen and hetero atom on its surface, so as to improve the parent on surface Electrically.And surface energy level increases and can capture electronics in semiconductor conduction band, you can change the electric property of material.Meanwhile it Other gases can be adsorbed, so as to which electric property be adjusted., can be in gaseous environment by the test to electric property Component sensed.After forming metal oxide nanotubes structure, specific surface area can be significantly increased, compared to molybdenum oxide Two dimensional crystal structure, specific surface area is higher, so as to enhance the absorption property of material.Molybdenum oxide nanotube is to micro NO2、 CO、CH4There are good sensitivity and selectivity Deng gas.Therefore, molybdenum oxide nanotube is a kind of air-sensitive material of great potential Material.
If in addition, prepare molybdenum oxide nanotube with the larger carbon nano pipe array of density, or directly by CNT knot Structure doped and compounded can form metal oxide nanotubes film in Electrochromic Molybdenum Oxide Coatings.The molybdenum oxide nanotube of formation is thin Film can be as the hole transmission layer of solar cell, then the transmission performance of transport layer can receiving due to molybdenum oxide nano-tube film Rice structure and be improved.
The embodiment of the present invention additionally provides a kind of metal oxide nanotubes, including：CNT and at least one layer of gold Belong to sull；Wherein,
At least one layer of metal-oxide film is deposited on the carbon nano tube surface；
The length of the CNT is 1cm~10cm.
Alternatively, a diameter of 1nm~4nm of the CNT.
Alternatively, the thickness of each layer metal-oxide film is 0.5nm~1.3nm.
Alternatively, the composition of the metal-oxide film includes：It is any one in molybdenum oxide, zinc oxide or tungsten oxide Kind.
Alternatively, a diameter of 2nm~15nm of the metal oxide nanotubes；
Alternatively, the metal oxide nanotubes have crystal lattice orientation；Wherein, it is brilliant in the metal-oxide film [001] crystal orientation of lattice is identical with the axial direction of the CNT, i.e., [001] crystal orientation of lattice is all the time along the axle of CNT To.
The embodiments of the invention provide a kind of preparation method of metal oxide nanotubes and metal oxide nanotubes, The overlength carbon nano pipe of Centimeter Level is prepared by chemical vapor deposition manner, then on the overlength carbon nano pipe surface prepared Depositing metal oxide film so that metal-oxide film wraps up whole CNT, forms Centimeter Level metal oxide and receives Mitron, substantially increase the length of oxide nano.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis These accompanying drawings obtain other accompanying drawings.
Fig. 1 is a kind of projection electron microscope for metal oxide nanotubes that one embodiment of the invention provides；
Fig. 2 is a kind of atomic force microscopy diagram for metal oxide nanotubes that one embodiment of the invention provides；
Fig. 3 is the atomic force microscopy diagram for another metal oxide nanotubes that one embodiment of the invention provides.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is Part of the embodiment of the present invention, rather than whole embodiments, based on the embodiment in the present invention, those of ordinary skill in the art The every other embodiment obtained on the premise of creative work is not made, belongs to the scope of protection of the invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.In following embodiments, institute Various kinds of equipment, reagent and the material used is that conventional commercial can obtain unless otherwise noted.
Below by several specific embodiments, the present invention is further illustrated.
Preparing the process of CNT mainly includes：
By photoetching process or paste method multiple slits are carved in substrate；
The ethanol solution of the metal chloride of any one in Fe, Mo, Cu and Cr or the aqueous solution are applied in substrate, so Substrate is placed in reactor afterwards, and reactor is heated to 800 DEG C~1000 DEG C, hydrogen or hydrogen are then passed through into reactor The mixed gas of gas and inert gas carries out reduction reaction, and metal nanoparticle is made；
Catalyst is made with metal nanoparticle, substrate is heated to 900 DEG C~1005 DEG C by reactor, and control carbon source The mixed gas of gas, hydrogen and vapor composition flows through substrate, among the slit on the substrate, grows 1cm ~10cm CNTs.
Preparing the process of metal oxide nanotubes mainly includes：
Solid metal oxide and the CNT are positioned in same sectional temperature-controlled reactor, wherein, it is described The first heating region that solid metal oxide is placed in the sectional temperature-controlled reactor, the CNT are placed in the segmentation Second heating region of temperature control reactor；
The temperature for controlling second heating region is 250 DEG C~350 DEG C, to be preheated to CNT；
The temperature for controlling first heating region is 500 DEG C~800 DEG C, and it is gas to make the solid metal oxide distillation State metal oxide, and the gas that reaction is not involved in described in utilization conveys the gaseous metal hydroxide of first heating region To second heating region；
The temperature for controlling second heating region is 450 DEG C~750 DEG C, further to the carbon nanometer after preheating Pipe is heated, and keeps the gaseous metal hydroxide to contact 1min~30min with the CNT, makes metal oxide Carbon nano tube surface is deposited on, forms at least one layer of metal-oxide film；
CNT is received with being deposited at least one layer of metal-oxide film composition metal oxide of carbon nano tube surface Mitron.
The process for preparing CNT is elaborated with several embodiments below and prepares metal oxide nanotubes Process.
Embodiment 1 is to illustrate by the use of metal iron nano-particle as catalyst preparation CNT, and made from utilizing CNT and molybdenum oxide powder prepare molybdenum oxide nanotube.
Embodiment 1：
Step A1：Using photoetching process, grade slit is set in substrate；
Step B1：The ethanol solution for the ferric trichloride that concentration is 0.02mol/L is applied in substrate, and trichlorine will be scribbled The substrate for changing the ethanol solution of iron is sent into quartz tube reactor, and the gaseous mixture of hydrogen and argon gas is passed through into quartz tube reactor Body and heated quartz pipe reactor, the flow velocity for controlling hydrogen is 200ml/min, and the flow velocity of argon gas is 400ml/min；When temperature liter During to 900 DEG C, constant temperature carries out reduction reaction 20min, and it is metal iron nano-particle to obtain particle diameter；
Step C1：The temperature of quartz tube reactor is risen to 1005 DEG C, now closes argon gas, and the flow velocity of hydrogen is changed For 70ml/min, while 20ml/min methane and the gaseous mixture of vapor are passed through, react 50min, obtain 10cm CNTs；
Step D1：CNT made from molybdenum oxide powder and step C1 is positioned in sectional temperature-controlled tube furnace, wherein, The substrate for being loaded with CNT is placed in the downstream of tube furnace, in the placed upstream molybdenum oxide powder of tube furnace.
Step E1：The temperature for adjusting tube furnace downstream is 300 DEG C, to be preheated to CNT, except carbon elimination nanometer The gas and other impurities adsorbed on pipe.
Step F1：The temperature for adjusting tube furnace upstream is 500 DEG C, and it is gaseous oxidation molybdenum to make molybdenum oxide powder sublimes, simultaneously The mixed airflow of 20ml/min hydrogen and argon gas is passed through, it is using the mixed airflow of hydrogen and argon gas that the gaseous oxidation molybdenum of distillation is defeated It is sent to the heating region in tube furnace downstream, i.e. CNT.
Step G1：The temperature for adjusting tube furnace downstream is 450 DEG C, and CNT is further heated, makes gaseous oxygen Change the slightly lower CNT of molybdenum Contact Temperature, and keep 10min.So that molybdenum oxide forms individual layer or more in carbon nano tube surface Layer Electrochromic Molybdenum Oxide Coatings, that is, form single wall or more wall molybdenum oxide nano tube structures.
The projection electron microscope of the molybdenum oxide nanotube of generation is as shown in figure 1, it can be seen that molybdenum oxide nanotube has Significantly through pavilion orientation, it is specific to illustrate that this is prepared by one kind all the time along the axial direction of CNT for [001] crystal orientation of lattice The new method of the nanotube of crystal lattice orientation.In addition, measuring the diameter of molybdenum oxide nanotube using AFM, its result is such as Shown in Fig. 2 and Fig. 3,4 layers of Electrochromic Molybdenum Oxide Coatings can be at most observed from figure, the thickness of each layer of metal-oxide film is 1.3nm, a diameter of 2nm~15nm of molybdenum oxide nanotube, a diameter of 1nm~4nm of internal layer CNT.
Embodiment 2：
Its course of reaction is similar to Example 1, when simply being preheated to CNT, by the temperature in tube furnace downstream It is adjusted to 250 DEG C.
Embodiment 3：
Its course of reaction is similar to Example 1, and the flow velocity for simply adjusting the mixed airflow of hydrogen and argon gas is 100ml/ min。
Embodiment 4：
Its course of reaction is similar to Example 1, when simply further being heated to CNT, by tube furnace downstream Temperature adjustment is 400 DEG C.
Embodiment 5：
Its course of reaction is similar to Example 1, CNT is in the atmosphere of gaseous oxidation molybdenum and argon gas, protects Hold 12min.
Embodiment 6 is to illustrate by the use of metal copper nano granules as catalyst preparation CNT, and made from utilizing CNT and Zinc oxide powder prepare zinc oxide nano mitron.
Embodiment 6：
Step A6：Using method of pasting, grade slit is set in substrate；
Step B6：The ethanol solution for the copper chloride that concentration is 0.5mol/L is applied in substrate, and copper chloride will be scribbled The substrate of ethanol solution be sent into quartz tube reactor, the mixed gas of hydrogen and argon gas is passed through into quartz tube reactor simultaneously Heated quartz pipe reactor, the flow velocity for controlling hydrogen are 200ml/min, and the flow velocity of argon gas is 500ml/min；When temperature rises to At 950 DEG C, constant temperature carries out reduction reaction 30min, obtains metal copper nano granules；
Step C6：The temperature of quartz tube reactor is risen to 1005 DEG C, now closes argon gas, and the flow velocity of hydrogen is changed For 160ml/min, while 80ml/min methane and the gaseous mixture of vapor are passed through, react 120min, obtain 1cm carbon nanometers Pipe；
Step D6：CNT made from Zinc oxide powder and step C6 is positioned in sectional temperature-controlled tube furnace, wherein, The substrate for being loaded with CNT is placed in the downstream of tube furnace, in the placed upstream Zinc oxide powder of tube furnace.
Step E6：The temperature for adjusting tube furnace downstream is 250 DEG C, to be preheated to CNT, except carbon elimination nanometer The gas and other impurities adsorbed on pipe.
Step F6：The temperature for adjusting tube furnace upstream is 800 DEG C, and it is gaseous oxidation zinc to make Zinc oxide powder distillation, simultaneously The mixed airflow of 100ml/min hydrogen and argon gas is passed through, using the mixed airflow of hydrogen and argon gas by the gaseous oxidation zinc of distillation It is transported to the heating region in tube furnace downstream, i.e. CNT.
Step G6：The temperature for adjusting tube furnace downstream is 750 DEG C, and CNT is further heated, makes gaseous oxygen Change the slightly lower CNT of zinc Contact Temperature, and keep 10min.So that zinc oxide forms individual layer or more in carbon nano tube surface Layer zinc-oxide film, that is, form single wall or more wall zinc oxide nano nanotube structures.
Embodiment 7：
Its course of reaction is similar to Example 6, and the flow velocity for simply adjusting the mixed airflow of hydrogen and argon gas is 40ml/min, And CNT is set to be in hydrogen with the atmosphere of argon gas and gaseous oxidation zinc, keeping 14min.
Embodiment 8：
Its course of reaction is similar to Example 6, when simply further being heated to CNT, by tube furnace downstream Temperature adjustment is 700 DEG C.
Embodiment 9：
Its course of reaction is similar to Example 6, and the temperature for simply adjusting tube furnace upstream is 850 DEG C, with when oxide powder and zinc End distillation is gaseous oxidation zinc.
Embodiment 10 is illustrating that the CNT prepared using embodiment 1 and tungsten oxide powder prepare tungsten oxide nanometer Pipe.
Embodiment 10：
Step A10 prepares the process of CNT to step C10, the process with the step A1 in embodiment 1 to step C1 Unanimously, will not be repeated here；
Step D10：CNT made from tungsten oxide powder and step C1 is positioned in sectional temperature-controlled tube furnace, its In, the substrate for being loaded with CNT is placed in the downstream of tube furnace, in the placed upstream tungsten oxide powder of tube furnace.
Step E10：The temperature for adjusting tube furnace downstream is 350 DEG C, to be preheated to CNT, except carbon elimination nanometer The gas and other impurities adsorbed on pipe.
Step F10：The temperature for adjusting tube furnace upstream is 700 DEG C, and it is gaseous oxidation tungsten to make tungsten oxide powder distillation, simultaneously 50ml/min argon gas is passed through, the gaseous oxidation tungsten of distillation is transported to tube furnace downstream using argon stream, be i.e. CNT Heating region.
Step G10：The temperature for adjusting tube furnace downstream is 600 DEG C, and CNT is further heated, makes gaseous oxygen Change the slightly lower CNT of tungsten Contact Temperature, and keep 15min.So that tungsten oxide forms individual layer or more in carbon nano tube surface Layer tungsten oxide film, that is, form single wall or more wall tungsten oxide nanometer tubular constructions.
Embodiment 11：
Its course of reaction is similar to Example 10, the flow velocity of argon gas simply is adjusted into 70ml/min, and make CNT In atmosphere in argon gas and gaseous state tungsten oxide, 25min is kept.
Embodiment 12：
Its course of reaction is similar to Example 10, when simply further being heated to CNT, by tube furnace downstream Temperature adjustment to 650 DEG C.
According to such scheme, various embodiments of the present invention at least have the advantages that：
1st, in embodiments of the present invention, the overlength carbon nano pipe of Centimeter Level is prepared by chemical vapor deposition manner, so Afterwards in the overlength carbon nano pipe surface depositing metal oxide film prepared so that metal-oxide film wraps up whole carbon and received Mitron, Centimeter Level metal oxide nanotubes are formed, substantially increase the length of oxide nano.Due to oxide nano The increase of length, the oxide nano prepared can be used for the application scenarios that electronics and micro-nano mechanical etc. become more meticulous.
2nd, in embodiments of the present invention, pre-add heat treatment is carried out to CNT, removes the gas adsorbed on CNT And other impurities, so that when metal oxide is deposited on carbon nano tube surface, the metal-oxide film of formation is more advised Whole, existing fault of construction is less.
3rd, in embodiments of the present invention, because the technology of preparing development of CNT is perfect, then prepared based on CNT The operating process very simple of metal oxide nanotubes, and condition is suitable, and metal oxide is in carbon nano tube surface The speed of growth is very fast, therefore is advantageous to rapid batch metaplasia production metal oxide nanotubes.
4th, in embodiments of the present invention, metal oxide is controlled to be deposited on CNT table in sectional temperature-controlled reactor Face, is advantageous to carry out solid metal oxide and CNT sectional temperature-controlled, makes the operation of preparation metal oxide nanotubes Process is simpler.
5th, in embodiments of the present invention, oxide nano is prepared using the metal oxide with excellent surface performance, The electric property of material can be changed, electric property can be also adjusted.After forming metal oxide nanotubes structure, Ke Yi great Width increases specific surface area, enhances the absorption property of material, therefore metal oxide nanotubes can be used as gas sensitive to micro Gas is detected.
6th, in embodiments of the present invention, using the absorption property of carbon nano tube surface, surface energy can be reduced, so as to favourable Nanotube is formed in auxiliary metallic oxide or other rigid two-dimensional materials.
It should be noted that herein, such as first and second etc relational terms are used merely to an entity Or operation makes a distinction with another entity or operation, and not necessarily require or imply and exist between these entities or operation Any this actual relation or order.Moreover, term " comprising ", "comprising" or its any other variant be intended to it is non- It is exclusive to include, so that process, method, article or equipment including a series of elements not only include those key elements, But also the other element including being not expressly set out, or also include solid by this process, method, article or equipment Some key elements.In the absence of more restrictions, the key element limited by sentence " including one ", is not arranged Except other identical factor in the process including the key element, method, article or equipment being also present.
It is last it should be noted that：Presently preferred embodiments of the present invention is the foregoing is only, is merely to illustrate the skill of the present invention Art scheme, is not intended to limit the scope of the present invention.Any modification for being made within the spirit and principles of the invention, Equivalent substitution, improvement etc., are all contained in protection scope of the present invention.

Claims (10)

  1. A kind of 1. preparation method of metal oxide nanotubes, it is characterised in that including：
    Slit is set on substrate；
    Catalyst is made with metal nanoparticle, the substrate is heated to 900 DEG C~1005 DEG C, and control carbon-source gas, hydrogen The substrate after heating, among the slit on the substrate, growth are flowed through with the mixed gas of vapor composition 1cm~10cm CNTs；
    At 250 DEG C~350 DEG C, the CNT is preheated；
    In the case where being not involved in the atmosphere protection of gas of reaction, metal oxide is deposited on the CNT table after preheating Face, form at least one layer of metal-oxide film；
    The CNT and at least one layer of metal-oxide film composition metal for being deposited on the carbon nano tube surface Oxide nano.
  2. 2. preparation method according to claim 1, it is characterised in that
    After the slit interstitial growth CNT on the substrate, the CNT is carried out described Before preheating, further comprise：
    Solid metal oxide and the CNT are positioned in same sectional temperature-controlled reactor, wherein, the solid-state The first heating region that metal oxide is placed in the sectional temperature-controlled reactor, the CNT are placed in described sectional temperature-controlled Second heating region of reactor；
    It is described that the CNT is preheated, including：The temperature for controlling second heating region is 250 DEG C~350 ℃。
  3. 3. preparation method according to claim 2, it is characterised in that
    The metal oxide is deposited on the carbon nano tube surface after preheating, including：
    The temperature for controlling first heating region is 500 DEG C~800 DEG C, makes the solid metal oxide distillation for gaseous state gold Belong to oxide, and the gaseous metal hydroxide of first heating region is delivered to institute by the gas that reaction is not involved in described in utilization State the second heating region；
    The temperature for controlling second heating region is 450 DEG C~750 DEG C, and further the CNT after preheating is entered Row heating, and keep the gaseous metal hydroxide to contact 10min~30min with the CNT.
  4. 4. preparation method according to claim 3, it is characterised in that
    The temperature for controlling second heating region is 450 DEG C~750 DEG C, including：Control second heating region Temperature is 500 DEG C~700 DEG C.
  5. 5. preparation method according to any one of claims 1 to 4, it is characterised in that
    The metal oxide includes：Any one in molybdenum oxide, zinc oxide or tungsten oxide.
  6. 6. method according to any one of claims 1 to 5, it is characterised in that
    The gas for being not involved in reaction includes：The mixed gas of argon gas or argon gas and hydrogen, flow velocity be 20ml/min~ 100ml/min, when the gas for being not involved in reaction is the mixed gas of argon gas and hydrogen, the hydrogen and the argon gas Volume parts ratio is 0.05~1.
  7. A kind of 7. metal oxide nanotubes prepared using any described method of claim 1 to 6, it is characterised in that bag Include：CNT and at least one layer of metal-oxide film；Wherein,
    At least one layer of metal-oxide film is deposited on the carbon nano tube surface；
    The length of the CNT is 1cm~10cm.
  8. 8. metal oxide nanotubes according to claim 7, it is characterised in that
    The thickness of each layer metal-oxide film is 0.5nm~1.3nm.
  9. 9. metal oxide nanotubes according to claim 7, it is characterised in that
    The composition of the metal-oxide film includes：Any one in molybdenum oxide, zinc oxide or tungsten oxide.
  10. 10. according to any described metal oxide nanotubes of claim 7 to 9, it is characterised in that
    A diameter of 2nm~15nm of the metal oxide nanotubes；
    And/or
    A diameter of 1nm~4nm of the CNT；
    And/or
    The metal oxide nanotubes have crystal lattice orientation；Wherein,
    [001] crystal orientation of lattice is identical with the axial direction of the CNT in the metal-oxide film.
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CN112736260A (en) * 2020-12-09 2021-04-30 中国科学院福建物质结构研究所 Composite material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104944404A (en) * 2014-03-26 2015-09-30 清华大学 Nano-tube film
CN106990266A (en) * 2017-04-26 2017-07-28 清华大学 It is a kind of to prepare needle point, the method for probe and needle point, probe
CN107101760A (en) * 2017-04-26 2017-08-29 清华大学 A kind of preparation method of precise torsion balance, precise torsion balance and application method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104944404A (en) * 2014-03-26 2015-09-30 清华大学 Nano-tube film
CN106990266A (en) * 2017-04-26 2017-07-28 清华大学 It is a kind of to prepare needle point, the method for probe and needle point, probe
CN107101760A (en) * 2017-04-26 2017-08-29 清华大学 A kind of preparation method of precise torsion balance, precise torsion balance and application method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112736260A (en) * 2020-12-09 2021-04-30 中国科学院福建物质结构研究所 Composite material and preparation method and application thereof

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