CN107324390B - Graphene oxide in-situ growth hollow structure nano tungsten oxide wire - Google Patents

Graphene oxide in-situ growth hollow structure nano tungsten oxide wire Download PDF

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CN107324390B
CN107324390B CN201710507356.8A CN201710507356A CN107324390B CN 107324390 B CN107324390 B CN 107324390B CN 201710507356 A CN201710507356 A CN 201710507356A CN 107324390 B CN107324390 B CN 107324390B
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graphene oxide
tungsten
wire
oxide
deionized water
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CN107324390A (en
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王长亮
田浩亮
汤智慧
郭孟秋
崔永静
高俊国
张欢欢
周子民
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AECC Beijing Institute of Aeronautical Materials
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Abstract

The invention discloses a hollow-structure nano tungsten oxide wire prepared by a graphene oxide in-situ growth method, which is prepared by mixing a certain amount of graphene oxide, a precursor compound containing tungsten, absolute ethyl alcohol and deionized water. Compared with the conventional preparation method of the high-pressure reaction kettle with the polytetrafluoroethylene lining, the preparation method has the advantages of low energy consumption, low cost, low industrial production investment and low product cost, and is convenient for realizing industrialized mass production.

Description

Graphene oxide in-situ growth hollow structure nano tungsten oxide wire
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a method for preparing a hollow-structure nano tungsten oxide wire by in-situ growth of graphene oxide.
Background
The nano tungsten oxide wire is a composite nano structure of a nano wire or a nano rod, and corresponding materials are prepared by scholars through processes of thermal evaporation, electrostatic spinning and the like at present, but the preparation methods relate to the problems of high temperature, high vacuum, high technical difficulty and the like, the preparation process for preparing the tungsten oxide nano wire in the traditional method is complex and large in energy consumption, the experimental conditions of the methods are harsh, the hydrothermal temperature of some methods is as high as 200 ℃, and the hydrothermal time is as long as 24 hours or even longer. In the conventional hydrothermal method, all reaction vessels used are high-pressure reaction kettles with polytetrafluoroethylene linings. The preparation method has high conditions and high energy consumption, and is contrary to the development of low power consumption, so that the research and development of the preparation method of the hollow structure nano tungsten oxide wire, which has the advantages of simple operation, low cost, controllable scale and high purity, is particularly important and urgent.
The graphene oxide has a single-layer structure with a nano-scale and is used as a carrier for preparing the nano tungsten oxide wire with the hollow structure, oxygen in the graphene oxide can be used as an oxygen source for generating tungsten oxide and can also consume carbon in the graphene, the nano tungsten oxide wire with the hollow structure can be grown in situ on the surface of the graphene oxide by controlling reaction conditions, the purity of the generated nano tungsten oxide wire with the hollow structure can be ensured, the scale uniformity of the generated nano tungsten oxide wire with the hollow structure can also be ensured by depending on the structural characteristics of the nano-sheet layer graphene, meanwhile, the process of growing the nano tungsten oxide wire with the hollow structure from the graphene oxide is a hollow nano tungsten oxide wire formed by curling the nano-sheet layer graphene oxide, the specific surface area of the nano tungsten oxide wire with the hollow structure is improved to a greater extent, and the adsorption and the characteristics of the nano tungsten oxide wire can be improved in multiples.
Accordingly, the prior art is deficient and needs improvement.
Disclosure of Invention
The invention aims to provide a hollow structure nano tungsten oxide wire prepared by graphene oxide in-situ growth, which has the advantages of simple operation, low cost, controllable scale, high purity and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hollow-structure nano tungsten oxide wire is prepared by a graphene oxide in-situ growth method, wherein the wire is prepared by mixing a certain amount of graphene oxide, a precursor compound containing tungsten, absolute ethyl alcohol and deionized water.
In the above, the precursor compound containing tungsten is a mixture of ammonium metatungstate and tungsten carbonyl, and the tungsten carbonyl in the mixture accounts for 1-5% of the mass of the ammonium metatungstate.
In the above, the graphene oxide and the tungsten-containing precursor compound have different molar ratios.
In the above, the graphene oxide is prepared by a redox method, and the mass ratio of the tungsten-containing precursor compound to the graphene oxide is 1: 1-6.
In the method, graphene oxide is wetted by a certain amount of absolute ethyl alcohol, and the mass percentage of the graphene oxide in the wetting solution is 0.1-0.5%; dispersing the mixture in a certain amount of deionized water, wherein the mass percent of the deionized water in the wetting solution is 5-8%; the ultrasonic treatment time is 30-180 min, and the ultrasonic frequency is 10-15 Hz. The amplitude rod is 10 mm.
Compared with the closest prior art, the invention has the following beneficial effects:
1) according to the technical scheme provided by the invention, the hollow-structure nano tungsten oxide wire is grown in situ on the surface of the nano lamellar graphene oxide, and the size, the shape and the composition of the hollow-structure nano tungsten oxide wire can be regulated and controlled by controlling the content ratio of reactants and reaction conditions.
2) Compared with the traditional methods of thermal evaporation, electrodeposition and the like for preparing the nano tungsten oxide wire, the method takes the nano lamellar graphene oxide as the carrier, exerts the characteristic of the nano monolayer structure of the graphene oxide, and in addition, directly grows in situ on the surface of the graphene oxide by controlling the reaction conditions, improves the nano-scale uniformity of the generated hollow structure nano tungsten oxide wire, and has higher purity.
3) Compared with other methods for preparing the nano tungsten oxide wire, the process provided by the invention takes the graphene oxide as the carrier, and the graphene oxide with a single-layer nano scale is curled to form the nano tungsten oxide wire with a hollow structure in the reaction process, so that the adsorption characteristic of the nano tungsten oxide wire as the adsorption of the polluted gas is multiplied by the hollow structure.
4) The process for preparing the hollow-structure nano tungsten oxide wire is simple, the graphene oxide and the tungsten-containing precursor mixture only need to be subjected to reduction reaction in the tubular reduction furnace, the cost is low, the production capacity is high, and the method is suitable for industrial batch production.
Drawings
FIG. 1 is an X-ray diffraction diagram of a graphene oxide in-situ growth hollow structure nano tungsten oxide line.
FIG. 2 is a scanning electron microscope image of a hollow structure nano tungsten oxide wire grown in situ by graphene oxide.
FIG. 3 is a transmission electron microscope image of graphene oxide in-situ grown hollow nano tungsten oxide.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a method for preparing a hollow-structure nano tungsten oxide wire by using a graphene oxide in-situ growth method, which is characterized by being prepared by mixing a certain amount of graphene oxide, a precursor compound containing tungsten, absolute ethyl alcohol and deionized water.
In the above, the precursor compound containing tungsten is a mixture of ammonium metatungstate and tungsten carbonyl, and the tungsten carbonyl in the mixture accounts for 1-5% of the mass of the ammonium metatungstate; so that the graphene oxide and the tungsten-containing precursor compound have different molar ratios. (ii) a The graphene oxide is prepared by adopting a redox method, and the mass ratio of the tungsten-containing precursor compound to the graphene oxide is 1: 1-6; the graphene oxide is wetted by a certain amount of absolute ethyl alcohol, and the mass percentage of the graphene oxide in the wetting solution is 0.1-0.5%; dispersing the mixture in a certain amount of deionized water, wherein the mass percent of the deionized water in the wetting solution is 5-8%; the ultrasonic treatment time is 30-180 min, and the ultrasonic frequency is 10-15 Hz. The amplitude rod is 10 mm.
The preparation method for preparing the hollow-structure nano tungsten oxide wire by the graphene oxide in-situ growth method comprises the following steps: a certain amount of graphite powder was added to a solution consisting of concentrated H2SO4(12mL), K2S2O8(2.5g) and P2O5(2.5g) and reacted at 80 ℃ for 4.5 hours. Then cooled to room temperature and 0.5L deionized water was added. And dried at normal temperature. This pre-oxidized graphite powder was added to 150mL of concentrated H2SO4, the environment was maintained at 0 ℃ with an ice-water bath, 15g of KMnO4 was gradually added while maintaining the temperature at 20 ℃ or less, and after the addition was completed, stirring was carried out at 35 ℃ for 2 hours. Then 250mL of deionized water was added and stirred for 2 hours. 0.7L of deionized water was then added, followed by 30 mL of 30% H2O2, dried at room temperature, and dialyzed against a dialysis bag for 1 week to remove the hetero-ions. And finally, carrying out vacuum filtration, and drying at normal temperature to obtain the graphene oxide.
Weighing 1g of graphene oxide, adding 1000g of absolute ethyl alcohol, uniformly stirring and mixing, adding 50g of deionized water for mixing, selecting a 10mm amplitude rod in an ultrasonic disperser, carrying out ultrasonic treatment for 30min at an ultrasonic frequency of 10Hz to obtain a mixed solution in which the graphene oxide is dispersed, weighing 99% of ammonium metatungstate and 1% of tungsten carbonyl by mass respectively to obtain a precursor mixture containing tungsten, weighing 1g of the precursor mixture containing tungsten, adding the precursor mixture into the dispersed solution of the graphene oxide, stirring for 30min, continuously dripping absolute ethyl alcohol in the stirring process, wherein the dripping amount is 18g, then carrying out suction filtration on the obtained precipitate, heating to 70 ℃ in an oven, drying for 10min, placing the obtained dry powder into an alumina crucible, introducing a certain amount of H2 in a tubular reduction furnace, introducing a certain amount of H2 with a flow rate of l00, heating to 900 ℃ at a heating rate of 70 ℃/min, and keeping the temperature for 1H, and finally introducing H2 to cool to room temperature to obtain the graphene oxide in-situ growth hollow structure nano tungsten oxide wire.
As shown in fig. 1, which is an XRD pattern of the graphene oxide in-situ grown hollow-structure nano tungsten oxide prepared in this example, it can be seen that all characteristic peaks in the pattern are completely consistent with the phase of tungsten oxide, and the surface is completely grown to WO phase.
Fig. 2 is a scanning electron microscope image of the graphene oxide in-situ grown hollow-structure nano tungsten oxide prepared in the example, and the hollow-structure nano tungsten oxide can be seen.
Fig. 3 is a transmission electron microscope image of the graphene oxide in-situ grown hollow-structure nano tungsten oxide prepared by the example, and it can be seen that the hollow-structure nano tungsten oxide line is 10-20nm, which proves that the hollow-structure nano tungsten oxide line has small scale and uniform distribution.
Example 2:
a certain amount of graphite powder was added to a solution consisting of concentrated H2SO4(12mL), K2S2O8(2.5g) and P2O5(2.5g) and reacted at 80 ℃ for 4.5 hours. Then cooled to room temperature and 0.5L deionized water was added. And dried at normal temperature. This pre-oxidized graphite powder was added to 150mL of concentrated H2SO4, the environment was maintained at 0 ℃ with an ice-water bath, 15g of KMnO4 was gradually added while maintaining the temperature at 20 ℃ or less, and after the addition was completed, stirring was carried out at 35 ℃ for 2 hours. Then 250mL of deionized water was added and stirred for 2 hours. 0.7L of deionized water was then added, followed by 30 mL of 30% H2O2, dried at room temperature, and dialyzed against a dialysis bag for 1 week to remove the hetero-ions. And finally, carrying out vacuum filtration, and drying at normal temperature to obtain the graphene oxide.
Weighing 2g of graphene oxide, adding 1000g of absolute ethyl alcohol, uniformly stirring and mixing, adding 60g of deionized water for mixing, selecting a 10mm amplitude rod in an ultrasonic disperser, carrying out ultrasonic treatment for 60min at an ultrasonic frequency of 12Hz to obtain a mixed solution in which the graphene oxide is dispersed, respectively weighing 99% of ammonium metatungstate and 1% of tungsten carbonyl by mass to obtain a precursor mixture containing tungsten, weighing 1g of the precursor mixture containing tungsten, adding the precursor mixture into the dispersed solution of the graphene oxide, stirring for 40min, continuously dripping absolute ethyl alcohol in the stirring process, wherein the dripping amount is 84g, then carrying out suction filtration on the obtained precipitate, heating the precipitate in an oven at 80 ℃, drying for 20min, placing the obtained dry powder in an alumina crucible, introducing a certain amount of H2 into a tubular reduction furnace at a flow rate of l00, heating to 1000 ℃ at a heating rate of 80 ℃/min, and keeping the temperature for 1H, and finally introducing H2 to cool to room temperature to obtain the graphene oxide in-situ growth hollow structure nano tungsten oxide wire.
Example 3:
a certain amount of graphite powder was added to a solution consisting of concentrated H2SO4(12mL), K2S2O8(2.5g) and P2O5(2.5g) and reacted at 80 ℃ for 4.5 hours. Then cooled to room temperature and 0.5L deionized water was added. And dried at normal temperature. This pre-oxidized graphite powder was added to 150mL of concentrated H2SO4, the environment was maintained at 0 ℃ with an ice-water bath, 15g of KMnO4 was gradually added while maintaining the temperature at 20 ℃ or less, and after the addition was completed, stirring was carried out at 35 ℃ for 2 hours. Then 250mL of deionized water was added and stirred for 2 hours. 0.7L of deionized water was then added, followed by 30 mL of 30% H2O2, dried at room temperature, and dialyzed against a dialysis bag for 1 week to remove the hetero-ions. And finally, carrying out vacuum filtration, and drying at normal temperature to obtain the graphene oxide.
Weighing 3g of graphene oxide, adding 1000g of absolute ethyl alcohol, uniformly stirring and mixing, adding 700g of deionized water for mixing, selecting a 10mm amplitude rod in an ultrasonic disperser, carrying out ultrasonic treatment for 120min at the ultrasonic frequency of 12Hz to obtain a mixed solution in which the graphene oxide is dispersed, weighing 99% of ammonium metatungstate and 1% of tungsten carbonyl by mass respectively to obtain a precursor mixture containing tungsten, weighing 1g of the precursor mixture containing tungsten, adding the precursor mixture into the dispersed solution of the graphene oxide, stirring for 50min, continuously dripping absolute ethyl alcohol in the stirring process, wherein the dripping amount is 168g, then carrying out suction filtration on the obtained precipitate, heating to 80 ℃ in an oven, drying for 20min, placing the obtained dry powder into an alumina crucible, introducing a certain amount of H2 in a tubular reduction furnace, introducing a certain amount of H2 with the flow rate of l00, heating to 1100 ℃ at the heating rate of 90 ℃/min, keeping the temperature for 2H, and finally introducing H2 to cool to room temperature to obtain the graphene oxide in-situ growth hollow structure nano tungsten oxide wire.
Example 4:
a certain amount of graphite powder was added to a solution consisting of concentrated H2SO4(12mL), K2S2O8(2.5g) and P2O5(2.5g) and reacted at 80 ℃ for 4.5 hours. Then cooled to room temperature and 0.5L deionized water was added. And dried at normal temperature. This pre-oxidized graphite powder was added to 150mL of concentrated H2SO4, the environment was maintained at 0 ℃ with an ice-water bath, 15g of KMnO4 was gradually added while maintaining the temperature at 20 ℃ or less, and after the addition was completed, stirring was carried out at 35 ℃ for 2 hours. Then 250mL of deionized water was added and stirred for 2 hours. 0.7L of deionized water was then added, followed by 30 mL of 30% H2O2, dried at room temperature, and dialyzed against a dialysis bag for 1 week to remove the hetero-ions. And finally, carrying out vacuum filtration, and drying at normal temperature to obtain the graphene oxide.
Weighing 4g of graphene oxide, adding 1000g of absolute ethyl alcohol, uniformly stirring and mixing, adding 800g of deionized water for mixing, selecting a 10mm amplitude rod in an ultrasonic disperser, carrying out ultrasonic treatment for 150min at an ultrasonic frequency of 15Hz to obtain a mixed solution in which the graphene oxide is dispersed, weighing 99% of ammonium metatungstate and 1% of tungsten carbonyl by mass respectively to obtain a precursor mixture containing tungsten, weighing 1g of the precursor mixture containing tungsten, adding the precursor mixture into the dispersed solution of the graphene oxide, stirring for 60min, continuously dripping absolute ethyl alcohol in the stirring process, wherein the dripping amount is 228g, then carrying out suction filtration on the obtained precipitate, heating to 90 ℃ in an oven, drying for 40min, placing the obtained dry powder into an alumina crucible, introducing a certain amount of H2 in a tubular reduction furnace, wherein the flow rate of H2 is l00, heating to 1200 ℃ at a heating rate of 100 ℃/min, keeping the temperature for 2H, and finally introducing H2 to cool to room temperature to obtain the graphene oxide in-situ growth hollow structure nano tungsten oxide wire.
Example 5:
a certain amount of graphite powder was added to a solution consisting of concentrated H2SO4(12mL), K2S2O8(2.5g) and P2O5(2.5g) and reacted at 80 ℃ for 4.5 hours. Then cooled to room temperature and 0.5L deionized water was added. And dried at normal temperature. This pre-oxidized graphite powder was added to 150mL of concentrated H2SO4, the environment was maintained at 0 ℃ with an ice-water bath, 15g of KMnO4 was gradually added while maintaining the temperature at 20 ℃ or less, and after the addition was completed, stirring was carried out at 35 ℃ for 2 hours. Then 250mL of deionized water was added and stirred for 2 hours. 0.7L of deionized water was then added, followed by 30 mL of 30% H2O2, dried at room temperature, and dialyzed against a dialysis bag for 1 week to remove the hetero-ions. And finally, carrying out vacuum filtration, and drying at normal temperature to obtain the graphene oxide.
Weighing 5g of graphene oxide, adding 1000g of absolute ethyl alcohol, uniformly stirring and mixing, adding 800g of deionized water for mixing, selecting a 10mm amplitude rod in an ultrasonic disperser, carrying out ultrasonic treatment for 150min at an ultrasonic frequency of 15Hz to obtain a mixed solution in which the graphene oxide is dispersed, weighing 99% of ammonium metatungstate and 1% of tungsten carbonyl by mass respectively to obtain a precursor mixture containing tungsten, weighing 1g of the precursor mixture containing tungsten, adding the precursor mixture into the dispersed solution of the graphene oxide, stirring for 60min, continuously dripping absolute ethyl alcohol in the stirring process, wherein the dripping amount is 286g, then carrying out suction filtration on the obtained precipitate, heating to 90 ℃ in an oven, drying for 40min, placing the obtained dry powder into an alumina crucible, introducing a certain amount of H2 in a tubular reduction furnace, wherein the flow rate of H2 is l00, heating to 1300 ℃ at a heating rate of 110 ℃/min, keeping the temperature for 2H, and finally introducing H2 to cool to room temperature to obtain the graphene oxide in-situ growth hollow structure nano tungsten oxide wire.
Example 6:
a certain amount of graphite powder was added to a solution consisting of concentrated H2SO4(12mL), K2S2O8(2.5g) and P2O5(2.5g) and reacted at 80 ℃ for 4.5 hours. Then cooled to room temperature and 0.5L deionized water was added. And dried at normal temperature. This pre-oxidized graphite powder was added to 150mL of concentrated H2SO4, the environment was maintained at 0 ℃ with an ice-water bath, 15g of KMnO4 was gradually added while maintaining the temperature at 20 ℃ or less, and after the addition was completed, stirring was carried out at 35 ℃ for 2 hours. Then 250mL of deionized water was added and stirred for 2 hours. 0.7L of deionized water was then added, followed by 30 mL of 30% H2O2, dried at room temperature, and dialyzed against a dialysis bag for 1 week to remove the hetero-ions. And finally, carrying out vacuum filtration, and drying at normal temperature to obtain the graphene oxide.
Weighing 6g of graphene oxide, adding 1000g of absolute ethyl alcohol, uniformly stirring and mixing, adding 800g of deionized water for mixing, selecting a 10mm amplitude rod in an ultrasonic disperser, carrying out ultrasonic treatment for 180min at an ultrasonic frequency of 15Hz to obtain a mixed solution in which the graphene oxide is dispersed, respectively weighing 99% of ammonium metatungstate and 1% of tungsten carbonyl by mass to obtain a precursor mixture containing tungsten, weighing 1g of the precursor mixture containing tungsten, adding the precursor mixture into the dispersed solution of the graphene oxide, stirring for 60min, continuously dripping absolute ethyl alcohol in the stirring process, dripping 324g of absolute ethyl alcohol, then carrying out suction filtration on the obtained precipitate, heating to 90 ℃ in an oven, drying for 40min, placing the obtained dry powder into an alumina crucible, introducing a certain amount of H2 in a tubular reduction furnace, introducing a certain amount of H2 at a flow rate of l00, heating to 1400 ℃ at a heating rate of 110 ℃/min, and (3) keeping the temperature for 3H, and finally introducing H2 to cool to room temperature to obtain the graphene oxide in-situ growth hollow structure nano tungsten oxide wire.
Compared with the closest prior art, the invention has the following beneficial effects:
1) according to the technical scheme provided by the invention, the hollow-structure nano tungsten oxide wire is grown in situ on the surface of the nano lamellar graphene oxide, and the size, the shape and the composition of the hollow-structure nano tungsten oxide wire can be regulated and controlled by controlling the content ratio of reactants and reaction conditions.
2) Compared with the traditional methods of thermal evaporation, electrodeposition and the like for preparing the nano tungsten oxide wire, the method takes the nano lamellar graphene oxide as the carrier, exerts the characteristic of the nano monolayer structure of the graphene oxide, and in addition, directly grows in situ on the surface of the graphene oxide by controlling the reaction conditions, improves the nano-scale uniformity of the generated hollow structure nano tungsten oxide wire, and has higher purity.
3) Compared with other methods for preparing the nano tungsten oxide wire, the process provided by the invention takes the graphene oxide as the carrier, and the graphene oxide with a single-layer nano scale is curled to form the nano tungsten oxide wire with a hollow structure in the reaction process, so that the adsorption characteristic of the nano tungsten oxide wire as the adsorption of the polluted gas is multiplied by the hollow structure.
4) The process for preparing the hollow-structure nano tungsten oxide wire is simple, the graphene oxide and the tungsten-containing precursor mixture only need to be subjected to reduction reaction in the tubular reduction furnace, the cost is low, the production capacity is high, and the method is suitable for industrial batch production.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.

Claims (1)

1. A hollow structure nanometer tungsten oxide wire is prepared by a graphene oxide in-situ growth method, and is characterized in that the wire is prepared by mixing a certain amount of graphene oxide, a precursor compound containing tungsten, absolute ethyl alcohol and deionized water; what is needed isThe precursor compound containing tungsten is a mixture of ammonium metatungstate and tungsten carbonyl, the graphene oxide is prepared by adopting a redox method, and the mass ratio of the precursor compound containing tungsten to the graphene oxide is 1:1 to 6; wetting graphene oxide by using a certain amount of absolute ethyl alcohol, wherein the mass percentage of the graphene oxide in a wetting solution is 0.1-0.5%, dispersing the graphene oxide in a certain amount of deionized water, the mass percentage of the deionized water in the wetting solution is 5-8%, carrying out ultrasonic treatment for 30-180 min, carrying out ultrasonic frequency of 10-15 Hz, and selecting an amplitude rod of 10mm to obtain a graphene oxide dispersion liquid; weighing 99% of ammonium metatungstate and 1% of tungsten carbonyl in percentage by mass to mix into a tungsten-containing precursor mixture, adding the tungsten-containing precursor mixture into graphene oxide dispersion liquid, stirring for 30-60 min, continuously dripping anhydrous ethanol into the mixture in the stirring process, wherein the dripping amount is 18-324 g, then carrying out suction filtration on the obtained precipitate, heating the precipitate in an oven at 70-90 ℃, and drying the precipitate for 10-40 min to obtain dry powder; the dry powder is placed in an alumina crucible, and a certain amount of H is introduced into a tubular reduction furnace2，H2Heating to 900-1400 ℃ at a heating rate of 70-110 ℃/min with a flow of l00sccm, keeping the temperature for 1-3H, and finally introducing H2And cooling to room temperature to obtain the graphene oxide in-situ growth hollow structure nano tungsten oxide wire.
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