CN105480966B - A method of spontaneous long graphene when reduction and carbonization tungsten in situ - Google Patents
A method of spontaneous long graphene when reduction and carbonization tungsten in situ Download PDFInfo
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- CN105480966B CN105480966B CN201510986444.1A CN201510986444A CN105480966B CN 105480966 B CN105480966 B CN 105480966B CN 201510986444 A CN201510986444 A CN 201510986444A CN 105480966 B CN105480966 B CN 105480966B
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
A method of spontaneous long graphene when reduction and carbonization tungsten in situ belongs to tungsten base and c-based nanomaterial technical field.The present invention passes through the tungsten source presoma substrate that becomes to be made of a large amount of nano particles by the existing horizontal substrate for preparing graphene, pass through carbon dissolution process of the tungsten source presoma in carbonisation, realize continuation molten carbon of the tungsten source presoma after being converted to tungsten carbide, since solid solution capacity of the tungsten carbide to carbon is lower, by the control of carbon amounts in control reaction system, it is made to realize absorption in tungsten carbide surface and growth graphene is precipitated.The device of the invention is easy, and raw material is simple and easy to get, low in cost, no pollution to the environment；It is passed through carbon source using in inert gas shielding, without obvious flammability hazard raw material；Product is easily handled, and high income, equipment is simple, semicontinuous can be operated, and mass production is suitable for.
Description
Technical field
It is specifically a kind of to go back in situ the present invention relates to the preparation method of a kind of tungsten base and c-based nanomaterial technical field
Carbon source is obtained by chemical vapour deposition technique when former tungsten carbide and adsorbs the side with the spontaneous long graphene of precipitation in nano grain surface
Method.
Background technique
Graphene is used as by sp2The carbon atom bonding of hydridization and the two-dimensional layer crystal structure formed, unique energy band
Structure and excellent electricity, calorifics, electromagnetism and mechanical property attract always the extensive concern of people, and are expected in future
More industrial circle obtains practical application.Since 2004, the property of graphene and application study have made great progress,
It is still important the asking of graphene researchers concern however, so far, how to prepare the graphene of high quality in large quantity
Topic.
The mechanical stripping method, graphite oxide reduction method, single-crystal metal or the silicon carbide epitaxy that develop at present and change
It learns the various preparation methods such as vapour deposition process and is not able to satisfy demand of the people to high-volume high-quality graphene.Through to existing literature
Retrieval side is existing, and the method for preparation high-quality amount mainly uses chemical vapour deposition technique, and X. Li et al. is in " Science " (science)
2009 the 324th the phase page 1312 to 1314 delivered " Large-area synthesis of high-quality and
Uniform graphene films on copper foils " (copper foil surface growing high quality large-area graphene), O. K.
Yu etc. is in " Applied Physics Letters " (applied physics flash report) the 93rd phase 11303-1 to 11303-3 page in 2008
On deliver " Graphene segregated on Ni surfaces and transferred to insulators " (nickel
Surface growth graphene is simultaneously transferred to insulator), Zou Zhiyu etc. is in " Chinese science: chemistry " the 1st phase page 1 to 17 upper hairs in 2013
Three texts such as table " chemical vapor deposition growth and process engineering of graphene are studied ", to chemical gaseous phase in this three documents
Sedimentation synthesizing graphite alkene has carried out comprehensive research and discussion.They are mainly by with the alloy of metallic nickel, copper or binary
Equal sheet metals or film are substrate as catalyst, have the principle of certain solubility to carbon by alloy of nickel, copper or binary etc., lead to
It crosses and carbon source is subjected to chemical gaseous phase decomposition, obtained carbon atom is dissolved and spread in metallic object phase, and temperature after preparation
Degree is precipitated inside metallic substrates during reducing, and prepares the graphene of high quality.However, so far, used in the method
Substrate be still continuous sheet metal or membranaceous for substrate, table of the carbon atom decomposited by various carbon sources in metallic substrates
Face diffusion and low temperature are precipitated to obtain and are deposited on the very thin graphene sample of substrate surface, are then turned by subsequent graphene film
It moves, it is made to be deposited on different surfaces.Since Metal Substrate bottom surface surface area is limited, it is lower to synthesize resulting graphene yield, cannot
Meet the needs of sizable application is to graphene product；On the other hand the synthesis cost of the method is relatively high, limits graphene
The large-scale application of product.
Summary of the invention
The purpose of the present invention is for chemical vapour deposition technique cannot be prepared on a large scale graphene the shortcomings that, proposition pass through by
The existing horizontal substrate for preparing graphene becomes the tungsten source presoma substrate being made of a large amount of nano particles, passes through tungsten source presoma
Carbon dissolution process in carbonisation realizes continuation molten carbon of the tungsten source presoma after being converted to tungsten carbide, due to tungsten carbide
It is lower to the solid solution capacity of carbon, by the control of carbon amounts in control reaction system, it is made to realize absorption in tungsten carbide surface and be precipitated
Grow graphene.Due to by limited horizontal substrate become nano particle composition surface so that the surface contacted with carbon at
The geometry order of magnitude increases, thus can largely prepare graphene.In addition, the device of the invention is easy, raw material is simple and easy to get, at low cost
It is honest and clean, no pollution to the environment；It is passed through carbon source using in inert gas shielding, without obvious flammability hazard raw material；Product is easily handled, and is received
Rate is high, and equipment is simple, semicontinuous can operate, and is suitable for mass production.
The purpose of the present invention is what is be achieved by the following technical programs, the present invention relates to a kind of reduction and carbonizations in situ
The method of spontaneous long graphene when tungsten, in turn includes the following steps:
Step 1: porcelain is added in 0.1-50 g solid nanometer tungsten source (nanometer wolframic acid powder or nano oxidized tungsten powder) first
Boat, and sample is laid in the surface of porcelain boat, the porcelain boat is pushed into horizontal high-temperature tubular reacting furnace later, by the two of tube furnace
End flange closure, and it is passed through inert gas in tube furnace arrival end, so that reaction system is in anaerobic state, inert gas flow
For 30-500 mL/min.
Step 2: horizontal high temperature process furnances are warming up to 400-600oC, by electronic peristaltic pump by second after heat preservation 1 hour
Alcohol/methanol solution (volume ratio 5:95) 10-50 mL is carried by inert gas and is input to level by the quartz ampoule that internal diameter is 2 mm
The high temperature reaction zone of high temperature process furnances, soaking time 1-2 hours.
Step 3: after the soaking time in step 2, horizontal high temperature process furnances are continuously heating to 900-1100oC, keep the temperature 2-8 h；After reaction, stop ethyl alcohol/methanol solution to be passed through, continue to be passed through inert gas, be cooled to 300 oC, close
Inert gas is closed, reacting furnace power supply is cut off, is cooled to room temperature, takes out porcelain boat and Collection and conservation sample.
Step 4: taking the sample 0.05-5 g in step 3 to be put into the vial of 20-250 mL, and 10-150 mL is added
Ethyl alcohol after, vial is sealed, carries out 12-24 hours ultrasonic disperses to it later.It is taken after dispersion upper in vial
Layer solution is filtered, dries graphene to get sheet, and the number of plies of graphene is 2-8 layers.
The present invention uses the reaction unit of chemical vapor deposition, dissolves carbon source using a large amount of small nano particles as substrate
Method can realize a large amount of preparations of high-quality graphene sample.Currently, the method for largely preparing graphene is mainly chemical oxidation
Method, and the method can substantially destroy graphite-structure, and introduce compared with polyfunctional group between graphite flake layer or surface, and the graphite flake number of plies
It is more, so that method preparation gained quality of graphene is not high；The chemical vapour deposition technique of preparation high-quality graphene uses at present
Be horizontal metal substrate, the growth of graphene is realized by the dissolution of the micro carbon sources of metallic substrates, due to the horizontal base of macroscopic view
Surface layer is less, it is difficult to realize the raised growth of graphene sample.Tungsten source presoma used in this method is carbonized in situ
Carbon dissolution in the process can realize the carbonization growth in situ of tungsten carbide, and effective control of carbon source is decomposited by ethyl alcohol/methanol solution
System input, so that the tungsten carbide sample after carbonization keeps nano-scale particle degree, to realize the geometry order of magnitude of growth substrate
Increase.With being surrounded around the nano silicon carbide tungsten particle after carbonization by carbon source, the tungsten carbide with micro carbon source solvability this
When start to dissolve carbon, as the temperature of subsequent reactions system reduces, dissolve in part carbon source in matrix and be precipitated in tungsten carbide surface
And obtain the graphene that the piece number of plies is less than 8 layers.Since the growth substrate in the reaction system is nanoscale, to make graphene
The substrate quantity geometry grade of growth increases, and yield greatly improved.On the other hand, since the reaction is real at a higher temperature
Existing, so that the graphene grown degree of graphitization with higher, surface is pure, and sample is not destroyed by external condition.
The invention has the following beneficial effects: the present invention use be carbonized after tungsten source presoma for growth substrate, with ethyl alcohol/
For methanol solution as liquid carbon source and solvent, raw material is simple and easy to get, low in cost.The solid-state carbon source phase of tungsten carbide is prepared with tradition
Than, it is easier to sample is permeated, keeps reaction efficiency higher；Compared with Conventional gaseous carbon source (methane, carbon monoxide and hydrogen), more
Add economy, convenient, safety；Compared with conventional organic solvents crack preparation gaseous carbon sources (methane, carbon monoxide and hydrogen), work
Skill is simpler.The present invention number of plies obtained is the mixing sample of 2-8 layers of graphene and tungsten carbide, due to tungsten carbide density
Height, graphene density is low, and the effective physical separation of the two can be achieved by subsequent dispersion.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of embodiment 1.
Specific embodiment
The present embodiment be premised on inventive technique scheme under implemented, give detailed embodiment and process,
But protection scope of the present invention is not limited to following embodiments.
Embodiment 1.
Porcelain boat is added in the solid nanometer wolframic acid of 1g first, and sample is laid in the surface of porcelain boat, later by the porcelain boat
It is pushed into horizontal high-temperature tubular reacting furnace, is passed through indifferent gas by the both ends flange closure of tube furnace, and in tube furnace arrival end
Body, makes reaction system be in anaerobic state, and inert gas flow is 100 mL/min.
Horizontal high temperature process furnances are warming up to 600oC, by electronic peristaltic pump by ethyl alcohol/methanol solution after heat preservation 1 hour
(volume ratio 5:95) 10 mL is carried the height that horizontal high temperature process furnances are input to by the quartz ampoule that internal diameter is 2 mm by inert gas
Warm reaction zone, soaking time 1 hour.
After soaking time, horizontal high temperature process furnances are continuously heating to 950 oC, keep the temperature 2h；After reaction, stop
Only ethyl alcohol/methanol solution is passed through, and is continued to be passed through inert gas, is cooled to 300 oC, inert gas is closed, reacting furnace power supply is cut off,
It is cooled to room temperature, takes out porcelain boat and Collection and conservation sample.
0.1 g of the sample being collected into is taken to be put into the vial of 20 mL, it is after the ethyl alcohol of 10 mL is added, vial is close
Envelope, carries out 12 hours ultrasonic disperses to it later.The upper solution in vial is taken to be filtered, dry after dispersion, i.e.,
The graphene of sheet is obtained, the number of plies of graphene is 2-8 layers.
Embodiment 2.
Porcelain boat is added in 2 g solid nanometer tungsten source (nanometer wolframic acid powder or nano oxidized tungsten powder) first, and sample is put down
It is laid on the surface of porcelain boat, the porcelain boat is pushed into horizontal high-temperature tubular reacting furnace later, by the both ends flange closure of tube furnace,
And it is passed through inert gas in tube furnace arrival end, so that reaction system is in anaerobic state, inert gas flow is 150 mL/min.
Horizontal high temperature process furnances are warming up to 600oC, by electronic peristaltic pump by ethyl alcohol/methanol solution after heat preservation 1 hour
(volume ratio 5:95) 15 mL is carried the height that horizontal high temperature process furnances are input to by the quartz ampoule that internal diameter is 2 mm by inert gas
Warm reaction zone, soaking time 1 hour.
After soaking time, horizontal high temperature process furnances are continuously heating to 900 oC, keep the temperature 2 h；After reaction,
Stop ethyl alcohol/methanol solution to be passed through, continues to be passed through inert gas, be cooled to 300 oC, close inert gas, cutting reacting furnace electricity
Source is cooled to room temperature, and takes out porcelain boat and Collection and conservation sample.
0.1 g of the sample being collected into is taken to be put into the vial of 50 mL, it is after the ethyl alcohol of 30 mL is added, vial is close
Envelope, carries out 24 hours ultrasonic disperses to it later.The upper solution in vial is taken to be filtered, dry after dispersion, i.e.,
The graphene of sheet is obtained, the number of plies of graphene is 2-8 layers.
Embodiment 3.
Porcelain boat is added in 5 g solid nanometer tungsten source (nanometer wolframic acid powder or nano oxidized tungsten powder) first, and sample is put down
It is laid on the surface of porcelain boat, the porcelain boat is pushed into horizontal high-temperature tubular reacting furnace later, by the both ends flange closure of tube furnace,
And it is passed through inert gas in tube furnace arrival end, so that reaction system is in anaerobic state, inert gas flow is 200 mL/min.
Horizontal high temperature process furnances are warming up to 400oC, by electronic peristaltic pump by ethyl alcohol/methanol solution after heat preservation 1 hour
(volume ratio 5:95) 50 mL is carried the height that horizontal high temperature process furnances are input to by the quartz ampoule that internal diameter is 2 mm by inert gas
Warm reaction zone, soaking time 2 hours.
After soaking time, horizontal high temperature process furnances are continuously heating to 1000 oC, keep the temperature 8 h；After reaction,
Stop ethyl alcohol/methanol solution to be passed through, continues to be passed through inert gas, be cooled to 300 oC, close inert gas, cutting reacting furnace electricity
Source is cooled to room temperature, and takes out porcelain boat and Collection and conservation sample.
0.5 g of the sample being collected into is taken to be put into the vial of 100 mL, it is after the ethyl alcohol of 50 mL is added, vial is close
Envelope, carries out 24 hours ultrasonic disperses to it later.The upper solution in vial is taken to be filtered, dry after dispersion, i.e.,
The graphene of sheet is obtained, the number of plies of graphene is 2-8 layers.
Embodiment 4.
Porcelain boat is added in 0.3 g solid nanometer tungsten source (nanometer wolframic acid powder or nano oxidized tungsten powder) first, and by sample
It is laid in the surface of porcelain boat, the porcelain boat is pushed into horizontal high-temperature tubular reacting furnace later, the both ends of tube furnace are sealed with flange
It closes, and is passed through inert gas in tube furnace arrival end, reaction system is made to be in anaerobic state, inert gas flow is 30 mL/
min。
Horizontal high temperature process furnances are warming up to 500oC, by electronic peristaltic pump by ethyl alcohol/methanol solution after heat preservation 1 hour
(volume ratio 5:95) 50 mL is carried the height that horizontal high temperature process furnances are input to by the quartz ampoule that internal diameter is 2 mm by inert gas
Warm reaction zone, soaking time 2 hours.
After soaking time, horizontal high temperature process furnances are continuously heating to 950 oC, keep the temperature 2 h；After reaction,
Stop ethyl alcohol/methanol solution to be passed through, continues to be passed through inert gas, be cooled to 300 oC, close inert gas, cutting reacting furnace electricity
Source is cooled to room temperature, and takes out porcelain boat and Collection and conservation sample.
0.2 g of the sample being collected into is taken to be put into the vial of 50 mL, it is after the ethyl alcohol of 30 mL is added, vial is close
Envelope, carries out 24 hours ultrasonic disperses to it later.The upper solution in vial is taken to be filtered, dry after dispersion, i.e.,
The graphene of sheet is obtained, the number of plies of graphene is 2-8 layers.
Embodiment 5.
Porcelain boat is added in 0.6 g solid nanometer tungsten source (nanometer wolframic acid powder or nano oxidized tungsten powder) first, and by sample
It is laid in the surface of porcelain boat, the porcelain boat is pushed into horizontal high-temperature tubular reacting furnace later, the both ends of tube furnace are sealed with flange
It closes, and is passed through inert gas in tube furnace arrival end, reaction system is made to be in anaerobic state, inert gas flow is 400 mL/
min。
Horizontal high temperature process furnances are warming up to 600oC, by electronic peristaltic pump by ethyl alcohol/methanol solution after heat preservation 1 hour
(volume ratio 5:95) 50 mL is carried the height that horizontal high temperature process furnances are input to by the quartz ampoule that internal diameter is 2 mm by inert gas
Warm reaction zone, soaking time 1.5 hours.
After soaking time, horizontal high temperature process furnances are continuously heating to 1100 oC, keep the temperature 2 h；After reaction,
Stop ethyl alcohol/methanol solution to be passed through, continues to be passed through inert gas, be cooled to 300 oC, close inert gas, cutting reacting furnace electricity
Source is cooled to room temperature, and takes out porcelain boat and Collection and conservation sample.
0.1 g of the sample being collected into is taken to be put into the vial of 50 mL, it is after the ethyl alcohol of 20 mL is added, vial is close
Envelope, carries out 24 hours ultrasonic disperses to it later.The upper solution in vial is taken to be filtered, dry after dispersion, i.e.,
The graphene of sheet is obtained, the number of plies of graphene is 2-8 layers.
Claims (2)
1. a kind of method of spontaneous long graphene when reduction and carbonization tungsten in situ, it is characterised in that: solid-state tungsten source is first placed in height
Warm reaction zone, while using ethyl alcohol/methanol solution as carbon source, using inert gas as protective gas and carrier gas carbon source fast speed belt
Enter high temperature reaction zone, in reaction zone, the carbon atom that carbon source decomposites makes tungsten source that carbonizing reduction reaction occur, and generates tungsten carbide；Tool
There is the tungsten carbide of micro carbon source solvability to start molten carbon at this time, as the temperature of subsequent reactions system reduces, dissolves in matrix
Part carbon source be precipitated that obtain the piece number of plies be 2-8 layers of graphene in tungsten carbide surface；Solid-state tungsten source is nanometer wolframic acid
Powder or nano oxidized tungsten powder；The volume ratio of ethanol solution and methanol solution in the ethyl alcohol/methanol solution is 5:95.
2. the method for spontaneous long graphene when a kind of reduction and carbonization tungsten in situ according to claim 1, characterized in that packet
Include following steps:
Step 1: being added porcelain boat for the solid nanometer tungsten source 0.1-50 g first, and sample is laid in the surface of porcelain boat, later
The porcelain boat is pushed into horizontal high-temperature tubular reacting furnace, by the both ends flange closure of tube furnace, and it is logical in tube furnace arrival end
Enter inert gas, reaction system is made to be in anaerobic state, inert gas flow is 30-500 mL/min；
Step 2: horizontal high temperature process furnances are warming up to 400-600oC, by electronic peristaltic pump by ethyl alcohol/methanol after heat preservation 1 hour
Solution 10-50 mL is anti-by the high temperature that inert gas carrying is input to horizontal high temperature process furnances by the quartz ampoule that internal diameter is 2 mm
Answer area, soaking time 1-2 hours；
Step 3: after the soaking time in step 2, horizontal high temperature process furnances are continuously heating to 900-1100 oC is protected
Warm 2-8 h；After reaction, stop ethyl alcohol/methanol solution to be passed through, continue to be passed through inert gas, be cooled to 300 oC is closed lazy
Property gas, cut off reacting furnace power supply, be cooled to room temperature, take out porcelain boat and Collection and conservation sample；
Step 4: it takes gained sample 0.05-5 g in step 3 to be put into the vial of 20-250 mL, is added 10-150 mL's
After ethyl alcohol, vial is sealed, 12-24 hours ultrasonic disperses is carried out to it later, the upper layer in vial is taken after dispersion
Solution is filtered, dries graphene product to get sheet, and the number of plies of graphene is 2-8 layers.
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