CN110465675A - A method of preparing the graphene that load has nanometer tungsten particle - Google Patents
A method of preparing the graphene that load has nanometer tungsten particle Download PDFInfo
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- CN110465675A CN110465675A CN201910706268.XA CN201910706268A CN110465675A CN 110465675 A CN110465675 A CN 110465675A CN 201910706268 A CN201910706268 A CN 201910706268A CN 110465675 A CN110465675 A CN 110465675A
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F9/26—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions using gaseous reductors
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Abstract
The present invention relates to a kind of methods for preparing load and having the graphene of nanometer tungsten particle, including the following steps: takes suitable ammonium metatungstate, DEXTROSE ANHYDROUS and NaCl, the Enough Dl water that can all dissolve NaCl is added, obtains homogeneous and transparent precursor solution；Freeze-drying, obtains drying solid powder, mixed-powder presoma is obtained after grinding；By powder precursor obtained in the previous step high-temperature calcination under atmosphere protection, atmosphere is hydrogen, is warming up to 700-780 DEG C, heat preservation a period of time, cooling down, obtains the self-assembly powder of the graphene-supported tungsten nano particle of three-dimensional sodium chloride-later；Self-assembly powder prepared by previous step is filtered using deionized water, removes NaCl, it is rear to be dried, obtain the graphene powder of load nanometer tungsten particle.
Description
Technical field
The invention belongs to the preparation technical fields of nano material, and in particular to the in-situ synthetic method of graphene and in graphite
The preparation method of supported nano-gold metal particles on alkene.
Technical background
Since graphene is found, due to the mechanical property with superelevation, excellent thermal conductivity and lower density
It is widely used in structural material and field of functional materials.For structural material field, the ideal tensile strength of graphene reaches
130GPa, elasticity modulus reach 1TPa, are applied in the metal-base composites such as copper-based, aluminium base or titanium-based as reinforced phase,
The intensity and elasticity modulus of material, the especially lower density of graphene can greatly be improved, makes it in enhancing light-weight metal
There is important value in the research field of based composites.
However, graphene in terms of improving composite property well below desired value, main cause is as follows: first, stone
There are stronger Van der Waals forces between black alkene, and reunion is easy to happen when graphene being caused to be added in metallic matrix, it is difficult to uniformly
Dispersion, and the graphene of this reunion crack initiation easily around in material deformation process deteriorate material property；Second,
Graphene usually has poor interface binding power with metallic matrix as a kind of carbon material, causes it in material deformation process
It is difficult to bearing load, is effectively played a role.In view of the above problems, researchers have found, the supported nano-gold category on graphene
Grain, can effectively solve the problem that the above problem.The reason is as follows that: metal nanoparticle can weaken the Van der Waals force between graphene, and one
Determine that the reunion behavior of graphene is inhibited on the other hand to select metal nanoparticle appropriate usually can be with Metal Substrate in degree
Diffusion bond or chemical bonding occur for body, to assist the interface binding power of raising graphene and matrix, therefore in graphene
Upper uniform load nano-metal particle is the technology with important research value and application prospect.
As the representative of refractory metal, tungsten has very big hardness and high fusing point, has in alloy and composite material
It is widely used and irreplaceable status, however, currently with high-temperature calcination fabricated in situ load nano-grade tungsten particle
The method of graphene, there is not yet relevant report.
Summary of the invention
The present invention is directed to propose a kind of method for the graphene for preparing supported nano-gold category tungsten particle, this method technique letter
Single, at low cost, simultaneously synthesizing tungsten particle Load Balanced, size are small, and graphene quality is high.Technical solution of the present invention is as follows:
A method of preparing the graphene that load has nanometer tungsten particle, including the following steps:
(1) suitable ammonium metatungstate ((NH is taken4)6H2W12O40·XH20), DEXTROSE ANHYDROUS (C6H12O6) and NaCl, it is added
The Enough Dl water that can all dissolve NaCl, obtains homogeneous and transparent precursor solution.
(2) precursor solution by previous step preparation is freeze-dried, and is obtained drying solid powder, is obtained mixed powder after grinding
Last presoma；
(3) by powder precursor obtained in the previous step high-temperature calcination under atmosphere protection, atmosphere is hydrogen, is warming up to 700-
780 DEG C, heat preservation a period of time, cooling down, obtains the self-assembly of the graphene-supported tungsten nano particle of three-dimensional sodium chloride-later
Powder；
(4) self-assembly powder prepared by previous step is filtered using deionized water, removes NaCl, afterwards at drying
Reason obtains the graphene powder of load nanometer tungsten particle.
In step (1), with W:C:NaCl molar ratio (1-1.8): 1:(100-300) weigh ammonium metatungstate ((NH4)6H2W12O40·XH20), DEXTROSE ANHYDROUS (C6H12O6) and NaCl.
In step (3), 50~100 DEG C/min of speed average out to of cooling down.
Compared with prior art, advantage of the process is that obtaining tungsten particle, thisization using ammonium metatungstate high-temperature calcination
The tungsten particle size of method preparation is small, Load Balanced；Tungsten particle can be securely fixed using the confinement effect of sodium chloride template
In graphene, make that there is stronger binding force between tungsten particle and graphene, furthermore this high-temperature calcination prepares graphene
It is at low cost, it can be mass-produced.
Detailed description of the invention
Fig. 1,2 are graphene SEM image prepared by the present invention
Fig. 3 is graphene TEM image prepared by the present invention
Fig. 4 is graphene XRD diagram picture prepared by the present invention
Fig. 5 is graphene Raman image prepared by the present invention
All attached drawings are 1 product characterization result of example.
The present invention does not address place and is suitable for the prior art.
Specific embodiment
The specific implementation example of preparation method of the present invention is given below.Example is only used for further illustrating preparation side of the invention
Method is not intended to limit the protection scope of the claim of this application.
Example 1
Sodium chloride 21.9g, glucose 0.601g are weighed, ammonium metatungstate 0.615g is placed in a beaker, and weighs 70mL deionization
Water, which pours into beaker, to be dissolved, magnetic agitation 6h, and uniformly mixed liquid is poured into culture dish, culture dish is then placed in refrigerator
It is freezed for 24 hours under the conditions of -20 DEG C of freezing chamber；Sample after freezing is put in freeze drier and is lyophilized, lyophilisation condition are as follows: -20 DEG C,
Freeze-drying time is for 24 hours.Sample after freeze-drying is ground to obtain presoma composite powder (powder diameter~100 mesh)；By precursor
End is placed in tube furnace, and in a hydrogen atmosphere (10 DEG C/min of heating rate, 750 DEG C of holding temperature, soaking time 2h, gas stream
Measure 200mL/min) high-temperature calcination, it is rapidly cooled to room temperature after heat preservation and (drops to 100 DEG C in 5min), by calcined powder
It is placed in 500ml beaker, 400ml deionized water is added, magnetic agitation 30min is fully dissolved in sodium chloride in water, then takes out
Filter, the powder that will be obtained after suction filtration are placed in 500ml beaker, and 400ml deionized water is added, and ultrasonic 10min is filtered again, will
Filtered sample is put into 70 DEG C of vacuum drying ovens dry 3h to get (W content is to the graphene powder for loading nanometer tungsten particle
10wt.%).
Example 2
Sodium chloride 21.9g, glucose 0.601g are weighed, ammonium metatungstate 0.307g is placed in a beaker, and weighs 70mL deionization
Water, which pours into beaker, to be dissolved, magnetic agitation 6h, and uniformly mixed liquid is poured into culture dish, culture dish is then placed in refrigerator
It is freezed for 24 hours under the conditions of -20 DEG C of freezing chamber；Sample after freezing is put in freeze drier and is lyophilized, lyophilisation condition are as follows: -20 DEG C,
Freeze-drying time is for 24 hours.Sample after freeze-drying is ground to obtain presoma composite powder (powder diameter~100 mesh)；By precursor
End is placed in tube furnace, and in a hydrogen atmosphere (10 DEG C/min of heating rate, 750 DEG C of holding temperature, soaking time 2h, gas stream
Measure 200mL/min) high-temperature calcination, it is rapidly cooled to room temperature after heat preservation and (drops to 100 DEG C in 5min), by calcined powder
It is placed in 500ml beaker, 400ml deionized water is added, magnetic agitation 30min is fully dissolved in sodium chloride in water, then takes out
Filter, the powder that will be obtained after suction filtration are placed in 500ml beaker, and 400ml deionized water is added, and ultrasonic 10min is filtered again, will
Filtered sample is put into 70 DEG C of vacuum drying ovens dry 3h to get (W content is to the graphene powder for loading nanometer tungsten particle
5wt.%).
Example 3
Sodium chloride 21.9g, glucose 0.601g are weighed, ammonium metatungstate 0.921g is placed in a beaker, and weighs 70mL deionization
Water, which pours into beaker, to be dissolved, magnetic agitation 6h, and uniformly mixed liquid is poured into culture dish, culture dish is then placed in refrigerator
It is freezed for 24 hours under the conditions of -20 DEG C of freezing chamber；Sample after freezing is put in freeze drier and is lyophilized, lyophilisation condition are as follows: -20 DEG C,
Freeze-drying time is for 24 hours.Sample after freeze-drying is ground to obtain presoma composite powder (powder diameter~100 mesh)；By precursor
End is placed in tube furnace, and in a hydrogen atmosphere (10 DEG C/min of heating rate, 750 DEG C of holding temperature, soaking time 2h, gas stream
Measure 200mL/min) high-temperature calcination, it is rapidly cooled to room temperature after heat preservation and (drops to 100 DEG C in 5min), by calcined powder
It is placed in 500ml beaker, 400ml deionized water is added, magnetic agitation 30min is fully dissolved in sodium chloride in water, then takes out
Filter, the powder that will be obtained after suction filtration are placed in 500ml beaker, and 400ml deionized water is added, and ultrasonic 10min is filtered again, will
Filtered sample is put into 70 DEG C of vacuum drying ovens dry 3h to get (W content is to the graphene powder for loading nanometer tungsten particle
15wt.%).
Claims (3)
1. a kind of method for preparing load and having the graphene of nanometer tungsten particle, including the following steps:
(1) suitable ammonium metatungstate ((NH is taken4)6H2W12O40·XH20), DEXTROSE ANHYDROUS (C6H12O6) and NaCl, addition can will
The Enough Dl water that NaCl all dissolves obtains homogeneous and transparent precursor solution.
(2) precursor solution by previous step preparation is freeze-dried, and drying solid powder is obtained, before obtaining mixed-powder after grinding
Drive body；
(3) by powder precursor obtained in the previous step high-temperature calcination under atmosphere protection, atmosphere is hydrogen, is warming up to 700-780
DEG C, heat preservation a period of time, cooling down, obtains the self-assembly powder of the graphene-supported tungsten nano particle of three-dimensional sodium chloride-later
End；
(4) self-assembly powder prepared by previous step is filtered using deionized water, removes NaCl, it is rear to be dried, it obtains
To the graphene powder of load nanometer tungsten particle.
2. the method according to claim 1, wherein in step (1), with W:C:NaCl molar ratio (1-1.8): 1:
(100-300) weighs ammonium metatungstate ((NH4)6H2W12O40·XH20), DEXTROSE ANHYDROUS (C6H12O6) and NaCl.
3. the method according to claim 1, wherein in step (3), the speed average out to 50 of cooling down~
100℃/min。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113636542A (en) * | 2021-08-25 | 2021-11-12 | 广西大学 | Method for preparing three-dimensional graphene from bottom to top |
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| US20070074601A1 (en) * | 2003-07-25 | 2007-04-05 | Korea Advanced Institute Of Science And Technology | Method of producing metal nanocomposite powder reinforced with carbon nanotubes and the powder prepared thereby |
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| CN105525124A (en) * | 2016-02-02 | 2016-04-27 | 天津大学 | Preparation method for in-situ synthesis of three-dimensional graphene-reinforced copper-based composite material |
| CN105562119A (en) * | 2015-12-22 | 2016-05-11 | 济宁学院 | Reduced graphene supported molybdenum or tungsten carbide catalyst and preparation method and application thereof |
| CN108480655A (en) * | 2018-04-10 | 2018-09-04 | 河南大学 | A kind of carbon-supported metal tungsten nano particle |
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- 2019-08-01 CN CN201910706268.XA patent/CN110465675A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2286792A1 (en) * | 1974-10-01 | 1976-04-30 | Ppg Industries Inc | Mono-tungsten carbide prodn. - from volatile tungsten cpd. and vapourised carbon source and calcination of solid prod. contg. di-tungsten carbide |
| US20070074601A1 (en) * | 2003-07-25 | 2007-04-05 | Korea Advanced Institute Of Science And Technology | Method of producing metal nanocomposite powder reinforced with carbon nanotubes and the powder prepared thereby |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113636542A (en) * | 2021-08-25 | 2021-11-12 | 广西大学 | Method for preparing three-dimensional graphene from bottom to top |
| CN113636542B (en) * | 2021-08-25 | 2023-01-10 | 广西大学 | Method for preparing three-dimensional graphene from bottom to top |
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