CN108585046B - A kind of high length-diameter ratio molybdenum dioxide nanotube and preparation method thereof - Google Patents
A kind of high length-diameter ratio molybdenum dioxide nanotube and preparation method thereof Download PDFInfo
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- CN108585046B CN108585046B CN201810369837.1A CN201810369837A CN108585046B CN 108585046 B CN108585046 B CN 108585046B CN 201810369837 A CN201810369837 A CN 201810369837A CN 108585046 B CN108585046 B CN 108585046B
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Abstract
The present invention relates to a kind of high length-diameter ratio molybdenum dioxide nanotubes and preparation method thereof, described method includes following steps: step (1) using four hydration ammonium heptamolybdates, monohydrate potassium prepares mixed solution as raw material and step (2) hydro-thermal reaction obtains high length-diameter ratio molybdenum dioxide nanotube.Nanotube content in high length-diameter ratio molybdenum dioxide nanotube of the invention is greater than 95%, and single nanotube diameter is 1-8nm, and length is 2-7 μm.The method of the present invention is nontoxic and pollution-free, environmental-friendly and repeated strong.
Description
Technical field
The invention belongs to semiconductor nano material technical fields, and in particular to a kind of high length-diameter ratio molybdenum dioxide nanotube and
Preparation method.
Background technique
Transition metal oxide has very unique performance, such as there are also piezoelectric effects etc. for superconductivity, giant magnetoresistance effect.
Wherein molybdenum dioxide has metallic conductivity, high-melting-point, and is expected to be widely used as catalyst, sensor, recording materials
And electrode material etc..
In the prior art, the method about synthesis molybdenum dioxide has very much.Typically closed by reduction molybdenum trioxide
At molybdenum dioxide powder.Yang etc. has obtained molybdenum dioxide by restoring molybdenum trioxide in alcohol steam.Manthiram and
Molybdenum dioxide powder has been made by the method for liquid-phase reduction in Liu et al..Not similar shape has been made by low-temperature hydrothermal reaction in Liang etc.
The molybdenum dioxide nano particle of looks.Also researcher synthesizes porous and hollow molybdenum dioxide nanometer by hydro-thermal method
Ball.The synthesis of one-dimensional molybdenum dioxide also has been reported that, but is to use carbon nanotube to be grown as template, or steam by heat mostly
The mode of hair synthesizes.For example, Zhou etc. is exactly to be received by being prepared for large-scale molybdenum dioxide in the progress thermal evaporation of Mo on piece
Mitron array.Suemitsu etc. in the mixed gas of acetylene and oxygen by lighting Mo substrate, to obtain molybdenum dioxide
Doughnut.However, being rarely reported the molybdenum dioxide nanotube that high yield high length-diameter ratio is made by low-temperature hydrothermal.
It is had a very important significance by the titanium dioxide molybdenum tube that high yield high length-diameter ratio is made in low-temperature hydrothermal.Of the invention
Inventor proposes the present invention by a large amount of creative works.
Summary of the invention
To solve the technical issues of above-mentioned background technique refers to, the present invention is intended to provide a kind of high length-diameter ratio molybdenum dioxide is received
Mitron and preparation method thereof, the especially method of low temperature preparation high length-diameter ratio molybdenum dioxide nanotube.Technical solution of the present invention
For a kind of preparation method of high length-diameter ratio molybdenum dioxide nanotube, include the following steps: step (1), with four hydration ammonium heptamolybdates,
Monohydrate potassium is raw material, prepares mixed solution；And step (2): hydro-thermal reaction.
It further, further include step (3) after step (2): by the product postprocessing after hydro-thermal reaction.
Further, the post-processing includes carrying out the product after hydro-thermal reaction to be centrifuged repeatedly washing and drying.
Further, the mixed solution is sufficiently stirred before step (2) hydro-thermal reaction, is subsequently placed in reaction kettle and carries out
Hydro-thermal reaction.
Further, in the step (1), the four hydrations ammonium heptamolybdate is placed in water, is stirred complete to ammonium molybdate
Fully dissolved in water, obtains ammonium molybdate solution；Monohydrate potassium is added into the ammonium molybdate solution during stirring,
Several hours are stirred, the mixed solution is obtained.It is preferred that stirring is completely dissolved in water for 10-30 minutes to ammonium molybdate.
In certain embodiment of the invention, the concentration of the ammonium molybdate solution is 0.01-0.08mol/L；In stirring
Monohydrate potassium is added into the ammonium molybdate solution in the process, stirs 1-8h, obtains the mixed solution；The ammonium molybdate
The concentration of solution is preferably 0.01-0.05mol/L, more preferable 0.025mol/L.
Further, the step (2) includes: that the mixed solution is transferred in ptfe autoclave, to anti-
It answers kettle to rise to 160-200 DEG C with the heating rate of 3-5 DEG C/min, keeps the temperature 40-60h, be then cooled to room temperature reaction kettle, anti-
It answers and carries out hydro-thermal reaction in kettle, hydro-thermal reaction 1-10h.It is preferred that rising to 180 DEG C with the heating rate of 5 DEG C/min, 48h is kept the temperature.
Further, in the step (3), the post-processing includes with deionized water and dehydrated alcohol in reaction kettle
Dark precipitate object carry out being centrifuged repeatedly washing, it is dry after the removal of impurity in object to be precipitated.
The present invention also provides molybdenum dioxide described in high length-diameter ratio molybdenum dioxide nanotube made from the above method to receive
Mitron is the molybdenum dioxide structure (monoclinic-MoO of monocline2), wherein nanotube content is greater than 95%, and single nanotube is straight
Diameter is 1-8nm, and length is 2-7 μm.
The present invention also provides the application of high length-diameter ratio molybdenum dioxide nanotube made from the above method, the height
The raw material that draw ratio molybdenum dioxide nanotube is prepared as semiconductor nano material.
The high length-diameter ratio molybdenum dioxide nanotube produced by the present invention is the molybdenum dioxide by monoclinic system
(monoclinic-MoO2) composition, wherein nanotube content is greater than 95%, and single nanotube diameter is 1-8nm, and length is 2-7 μ
m.The molybdenum dioxide of method preparation monocline (crystallographic system) provided by the invention has high length-diameter ratio, high-purity and high-crystallinity, simultaneously
The preparation method is nontoxic and pollution-free, environmental-friendly and repeated strong, to a large amount of preparations of high crystalline high activity molybdenum dioxide with
Industrial applications are of great significance.This is provided for the preparation of One, Dimensional Semiconductor Nano Materials and subsequent nano material volume production
A possibility that more.
Detailed description of the invention
Fig. 1 is molybdenum dioxide made from the corresponding method of 0.01mol/L ammonium molybdate solution (hydrothermal reaction at low temperature) in the present invention
The transmission electron microscope picture of nanotube；
Fig. 2 is molybdenum dioxide made from the corresponding method of 0.01mol/L ammonium molybdate solution (hydrothermal reaction at low temperature) in the present invention
The X-ray diffractogram of nanotube.
Specific embodiment
Embodiments of the present invention are described more detail below, an embodiment of the invention is a kind of high length-diameter ratio two
The preparation method of molybdenum oxide nanotube includes the following steps: step (1), is original with four hydration ammonium heptamolybdates, monohydrate potassium
Material, prepares mixed solution；And step (2): hydro-thermal reaction.
The preparation method of this embodiment of the present invention is a kind of preparation method of high length-diameter ratio molybdenum dioxide nanotube, especially
It is the method for low temperature preparation high length-diameter ratio molybdenum dioxide nanotube.
It further include step (3): after the product after hydro-thermal reaction after step (2) in the embodiment of the invention
Processing.
In the embodiment, the post-processing includes carrying out the product after hydro-thermal reaction to be centrifuged repeatedly washing and drying.
In the embodiment, the mixed solution is sufficiently stirred before step (2) hydro-thermal reaction, is subsequently placed in reaction kettle
Carry out hydro-thermal reaction.
In the embodiment of the invention, in the step (1), the four hydrations ammonium heptamolybdate is placed in water,
Stirring is completely dissolved in water for 10-30 minutes to ammonium molybdate, obtains ammonium molybdate solution；To the ammonium molybdate during stirring
Monohydrate potassium is added in solution, stirs several hours, obtains the mixed solution.
In certain embodiment of the invention, the concentration of the ammonium molybdate solution is 0.01-0.0gmol/L；In stirring
Monohydrate potassium is added into the ammonium molybdate solution in the process, stirs 1-8h, obtains the mixed solution；The ammonium molybdate
The concentration of solution is preferably 0.01-0.05mol/L, more preferable 0.025mol/L.
Further, the step (2) includes: that the mixed solution is transferred in ptfe autoclave, to anti-
It answers kettle to rise to 160-200 DEG C with the heating rate of 3-5 DEG C/min, keeps the temperature 40-60h, be then cooled to room temperature reaction kettle, anti-
It answers and carries out hydro-thermal reaction in kettle, hydro-thermal reaction 1-10h.It is preferred that rising to 180 DEG C with the heating rate of 5 DEG C/min, 48h is kept the temperature.
Further, in the step (3), the post-processing includes with deionized water and dehydrated alcohol in reaction kettle
Dark precipitate object carry out being centrifuged repeatedly washing, after the removal of impurity in object to be precipitated, height described in substance drying to obtain is grown
Diameter is than molybdenum dioxide nanotube.
It is the molybdenum dioxide structure of monocline the present invention also provides molybdenum dioxide nanotube made from the above method,
Middle nanotube content is greater than 95%, and single nanotube diameter is 1-8nm, and length is 2-7 μm.
The present invention also provides the application of high length-diameter ratio molybdenum dioxide nanotube made from the above method, the height
The raw material that draw ratio molybdenum dioxide nanotube is prepared as semiconductor nano material.
The high length-diameter ratio molybdenum dioxide nanotube produced by the present invention is by the molybdenum dioxide of monocline (crystallographic system)
(monoclinic-MoO2) composition, wherein nanotube content is greater than 95%, and single nanotube diameter is 1-8nm, and length is 2-7 μ
m.The molybdenum dioxide of method preparation monocline (crystallographic system) provided by the invention has high length-diameter ratio, high-purity and high-crystallinity, simultaneously
The preparation method is nontoxic and pollution-free, environmental-friendly and repeated strong, to a large amount of preparations of high crystalline high activity molybdenum dioxide with
Industrial applications are of great significance.This is provided for the preparation of One, Dimensional Semiconductor Nano Materials and subsequent nano material volume production
A possibility that more.
Below with reference to embodiment, the present invention is further illustrated:
Embodiment 1
1) ammonium molybdate solution of 0.01mol/L is prepared respectively；Stirring 15min ammonium molybdate is completely dissolved in water, continuous
It is separately added into monohydrate potassium into above-mentioned ammonium molybdate solution during stirring, stirs several hours, to two kinds of reactants
It is uniformly mixed；2) mixed solution is transferred in ptfe autoclave.To reaction kettle with the heating rate liter of 5 DEG C/min
To 180 DEG C, 48h is kept the temperature.Then reaction kettle is cooled to room temperature.3) then, with deionized water and dehydrated alcohol in reaction kettle
Dark precipitate object carry out centrifuge washing repeatedly, after the impurity removal in object to be precipitated, by substance drying to obtain titanium dioxide
Molybdenum nanotube.
The transmission electron microscope picture of the resulting high length-diameter ratio molybdenum dioxide nanotube is as shown in Fig. 1, and X-ray diffractogram is such as
Shown in attached drawing 2.
Transmission electron microscope picture by the high length-diameter ratio molybdenum dioxide nanotube is as shown in Fig. 1, X-ray diffractogram such as attached drawing
It can be seen that shown in 2, the molybdenum dioxide of preparation monocline (crystallographic system) has high length-diameter ratio, high-purity and high-crystallinity.Again due to the system
Preparation Method is nontoxic and pollution-free, environmental-friendly and repeated strong, thus to a large amount of preparations of high crystalline high activity molybdenum dioxide with
Industrial applications are of great significance.It is provided more for the preparation and subsequent nano material volume production of One, Dimensional Semiconductor Nano Materials
A possibility that more.
Embodiment 2
1) ammonium molybdate solution of 0.025mol/L is prepared；Stirring 30min ammonium molybdate is completely dissolved in water, is being stirred continuously
During be separately added into monohydrate potassium into above-mentioned ammonium molybdate solution, stir several hours, mixed to two kinds of reactants
Uniformly；2) mixed solution is transferred in ptfe autoclave.It is risen to reaction kettle with the heating rate of 3 DEG C/min
200 DEG C, keep the temperature 45h.Then reaction kettle is cooled to room temperature.3) then, with deionized water and dehydrated alcohol in reaction kettle
Dark precipitate object carries out centrifuge washing repeatedly, after the impurity removal in object to be precipitated, by substance drying to obtain molybdenum dioxide
Nanotube.
It is analyzed and equally learns that the high length-diameter ratio molybdenum dioxide nanotube of method preparation of the invention is monocline (crystallographic system)
Molybdenum dioxide has high length-diameter ratio, high-purity and high-crystallinity.The preparation method is nontoxic and pollution-free, environmental-friendly and repeated
By force, therefore to a large amount of preparations of high crystalline high activity molybdenum dioxide and industrial applications it is of great significance.It is partly led to be one-dimensional
The preparation of body nano material and subsequent nano material volume production provide a possibility that more.
It will be appreciated by those skilled in the art that the invention is not limited to the specific embodiments described herein, to those skilled in the art
It is able to carry out various apparent variations for member, readjusts and substitutes without departing from protection scope of the present invention.Therefore, though
So the present invention has been described in more detail through the above examples, but the present invention is not limited to the above embodiments only,
It without departing from the inventive concept, can also include more other equivalent embodiments, and the scope of the present invention is by appended
Scope of the claims determine.
Claims (6)
1. a kind of preparation method of high length-diameter ratio molybdenum dioxide nanotube, which comprises the steps of:
Step (1) prepares mixed solution using four hydration ammonium heptamolybdates, monohydrate potassium as raw material；
And step (2): the mixed solution is transferred in ptfe autoclave, to reaction kettle with 3- by hydro-thermal reaction
The heating rate of 5 DEG C/min rises to 160-200 DEG C, keeps the temperature 40-60h, is then cooled to room temperature reaction kettle, in a kettle into
Row hydro-thermal reaction, hydro-thermal reaction 1-10h obtain high length-diameter ratio molybdenum dioxide nanotube；
Wherein, in the step (1), the four hydrations ammonium heptamolybdate is placed in water, stirring is dissolved completely in ammonium molybdate
In water, ammonium molybdate solution is obtained；The concentration of the ammonium molybdate solution is 0.01-0.025mol/L；To institute during stirring
It states and monohydrate potassium is added in ammonium molybdate solution, stir 1-8h, obtain the mixed solution.
2. the method as described in claim 1, which is characterized in that
It further include step (3) after step (2): by the product postprocessing after hydro-thermal reaction.
3. method according to claim 2, which is characterized in that
The post-processing includes carrying out the product after hydro-thermal reaction to be centrifuged repeatedly washing and drying.
4. method as claimed in claim 3, which is characterized in that
In the step (3), the post-processing includes with deionized water and dehydrated alcohol to the dark precipitate object in reaction kettle
It carries out being centrifuged repeatedly washing, after the impurity removal in object to be precipitated, by high length-diameter ratio molybdenum dioxide described in substance drying to obtain
Nanotube.
5. the high length-diameter ratio molybdenum dioxide nanotube as made from any one of claim 1-4 the method, which is characterized in that described
Molybdenum dioxide nanotube is the molybdenum dioxide structure of monoclinic system, and wherein nanotube content is greater than 95%, and single nanotube diameter is
1-8 nm, length are 2-7 μm.
6. as described in the high length-diameter ratio molybdenum dioxide nanotube made from any one of claim 1-4 the method or claim 5
High length-diameter ratio molybdenum dioxide nanotube application, which is characterized in that the high length-diameter ratio molybdenum dioxide nanotube is as half
The raw material of conductor nano material preparation.
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2018
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| JPS63222015A (en) * | 1987-03-12 | 1988-09-14 | Agency Of Ind Science & Technol | Production of molybdenum dioxide from molybdate-containing aqueous solution |
| CN101780981A (en) * | 2009-01-14 | 2010-07-21 | 新疆教育学院 | Hydro-thermal synthesis method of molybdenum dioxide nano particle |
| CN105836715A (en) * | 2016-03-25 | 2016-08-10 | 合肥工业大学 | Self-assembly ternary sulfur molybdenum selenide nanotube with controllable composition and preparation method thereof |
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