CN108928810A - NaOH reconfigures the strong new application for preparing nano-carbon material of C-C - Google Patents
NaOH reconfigures the strong new application for preparing nano-carbon material of C-C Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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Abstract
NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, is realized by following methods：In 600 DEG C -900 DEG C of inert gas environment, carbon material is mixed in the molten state with NaOH, the C-C in carbon material is reconfigured in mixed process in the molten state, the nano material of diamond carbon basket structure, the nano material of the diamond carbon basket structure constitutes diamond carbon basket structure by ten carbon atoms, the diamond carbon basket structure is to delete the carbon atom on eight vertex in square body diamond structure cell, and remaining ten carbon atoms constitute diamond carbon basket structure.
Description
Technical field
The invention belongs to field of new materials, and the C-C for specially reconfiguring carbon material with NaOH is strong to prepare novel nano carbon
The purposes of material and the novel nano carbon material.
Background technique
In recent years, the research of carbon nanotechnology is quite active, diversified nano-sized carbon crystallization, needle-shaped, rodlike, tubbiness etc.
It emerges one after another.Germany in 2000 and American scientist also prepare the hollow caged molecule being made of 20 carbon atoms.According to reason
It comprising 20 carbon atoms is made of regular pentagon by reckoning, C60 molecule is the smallest by one in fowler ethylenic structural molecule
Kind, it is contemplated that former in the angle combined, dynamics the problems such as, people think that always this kind of molecule is very unstable, it is difficult to exist.
It is that materialogy field solves an important research topic that moral, beautiful scientist, which have produced C60 caged molecule,.In carbon nanomaterial
The new carbons such as carbon nano-fiber, carbon nanotubes have many excellent physics and chemical characteristic, are widely used in all
It is multi-field.
Carbon be present in nature with the mankind are most closely related, one of most important element, it have SP, SP2,
The multiple electronic orbital characteristics of SP3 hydridization, the anisotropy of SP2 in addition cause crystal each guide property and other arrangements it is each to
The property led.Therefore there is miscellaneous property with the carbon materials that carbon is unique constitution element, and new carbon is harmonious newly
Carbon materials are also constantly found and are manually made.In fact, can be used as single-element can shape as carbon without any element
Imaging three-dimensional diamond crystal, two-dimentional graphite synusia, one-dimensional Cabbeen and carbon nanotube, zero dimension fullerene molecule etc. are so many
The entirely different substance of structure and properties.Various typical organic matters, the inorganic matter that table 1 gives the chemical bonding of carbon and its formed
With the example of carbon phase.
Scientists gradually find carbon materials hardness, optical characteristics, heat resistance nano-carbon material, radiation hardness characteristic,
Chemical-resistant resistance characteristic, electrical insulating property, electric conductivity, surface and interfacial characteristics etc. are more excellent than other materials, it may be said that carbon materials
Material almost includes characteristic possessed by all substances on the earth, such as most hard-most soft, insulator-semiconductor-good conductor, absolutely
Heat-good thermally conductive, full extinction-full impregnated light etc., therefore tool has been widely used,
Type
(1) Carbon nanotubes are nano-carbon material is rolled by the graphene sheet layer that carbon atom is formed seamless, hollow
Tube body generally can be divided into single-walled carbon nanotube, multi-walled carbon nanotube and double-walled carbon nano-tube.
(2) carbon fiber is divided into acrylic carbon fibre and two kinds of asphalt-based carbon fiber.Carbon fiber is light to be strongly higher than steel in aluminium,
Its specific gravity is the 1/4 of iron, is strongly 10 times of iron, other than having superb strength, chemical property is highly stable, corrosion-resistant
Property high, while high temperature resistant and low temperature, radiation hardness, smelly eliminating.Carbon fiber can be used in a variety of different fields, due to manufacturing cost
Height, be largely used to air material, sports apparatus, architectural engineering structural material.Invent a kind of honest and clean in University of Illinois of the U.S.
Valence carbon fiber has the toughness of high-tenacity, while having the gas and harmful biology of very powerful adsorption capacity, energy filtering poisonous,
It can be used for manufacturing protective clothing, mask, gloves and protective clothing etc..
(3) carbon ball is divided by carbon ball according to size：(1) fullerene family Cn and onion carbon (have closed graphite
Layer structure, diameter is between 2-20nm), such as C60, C70 etc.；(2) incomplete graphited nano carbon microsphere, diameter is in 50nm 1
Between μm；(3) carbon microballon, diameter is at 11 μm or more.In addition, hollow carbon sphere, solid hard can be divided into according to the structure and morphology of carbon ball
Carbon ball, porous carbon ball, core-shell structure carbon ball and gluey carbon ball etc..
（1）Laser evaporation graphite method：The method is using metallic catalyst, with pulsed laser ablation graphite
Surface generates nano-scale carbon material in graphite surface.
（2）Plasma spray deposition method：The method is the tungsten electrode (cathode) and copper electrode (anode) for spraying ion
It is cooling to carry out water, after Ar/He carrier gas carries under one's arms benzene vapor by plasma torch, can be deposited on the surface of anode containing receiving
The carbon ash of meter level carbon material.
（3）The electrolytically generated method of condensed phase：It uses graphite electrode (electrolytic cell is anode), temperature and argon at about 600 DEG C
Under conditions of gas shielded, with the electrolyzing fused halogenation alkali salt of certain voltage and current, electrolytically generated various informative carbon is received
Rice material.
（4）Graphite acr method：Graphite acr method is discharged in certain atmosphere with graphite electrode, is received from cathode deposition
Collect the method for carbon nanomaterial.
（5）Chemical vapour deposition technique：It is to prepare the widely used method of carbon material institute, it can be divided into again catalytic chemistry gas
It mutually deposits and without catalytic chemical gaseous phase deposition.Catalysis point is carried out when gas (or steam) containing carbon source is flowed through catalyst surface
Solution.Ethylene, acetylene, styrene, benzene, toluene, methane etc. are typically used as carbon source, these are typically all that chemical property is more active
Compound containing unsatisfied chemical bond；Transition metal, rare metal or metal oxide are commonly used as catalyst；Argon gas, nitrogen
Gas or hydrogen etc. are typically used as carrier gas.No catalyzed gas deposition does not have to any catalyst then, directly thermally decomposes under protective atmosphere
Gas phase carbonaceous organic material.
In conclusion the above-mentioned method for preparing nano-carbon material, implements under than relatively hazardous environment, and do not have
The condition of industrialized production.
Summary of the invention
Present invention solves the technical problem that being in the environment of being safe from danger factor, to carry out industrialized production nano carbon material
Material.
The invention is realized in this way：NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, by following methods
It realizes：In 600 DEG C -900 DEG C of inert gas environment, carbon material is mixed in the molten state with NaOH, in molten condition
Under mixed process in the C-C in carbon material is reconfigured, formed carbon nanomaterial.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, and the carbon material is 8-12 moles
The carbon material of aromatic ring structure mixes in the molten state with 6-10 moles of NaOH, and temperature range is 700 DEG C -800 DEG C.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, and the carbon material is 8-12 moles
Plant fiber charing material mixed in the molten state with 6-10 moles of NaOH, temperature range be 700 DEG C -800 DEG C.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, after the plant fiber charing
Material is coal dust.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, after the plant fiber charing
Material is solid carbonaceous material of the plant fiber after 700 DEG C of -800 DEG C of pyrolysis.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, after the plant fiber charing
Material is solid carbonaceous material of the plant fiber after 700 DEG C of -800 DEG C of pyrolysis, is pyrolyzed as further in 700 DEG C -800 DEG C of inertia
In gaseous environment, dry papermaking wood pulp is sprayed into, papermaking wood pulp is pyrolyzed, the solid carbonaceous material after pyrolysis falls into molten condition
The solid carbonaceous material for being pyrolyzed the NaOH of molten condition with papermaking wood pulp mixes.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, and the carbon material and NaOH are and iron
It is carried out in the environment of atomic contacts.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, and the carbon material and NaOH are and iron
It carries out in the environment of atomic contacts, is mixed in iron container for the NaOH of molten condition with carbon material；Product is concentrated in into water
And crystallize at normal temperature, collect the crystal that crystalline solid is carbon nanomaterial, referred to as diamond carbon cage acid sodium crystal.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, described that diamond carbon cage acid sodium is brilliant
Body is heated to color and fades to grey black, and grey black solids is the nano material of diamond carbon basket structure.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, and the carbon material and NaOH are and iron
It carries out in the environment of atomic contacts, is mixed for the NaOH of molten condition with addition iron powder in carbon material mixture；Product is dense
It shrinks in water and crystallizes at normal temperature, collect the crystal that crystalline solid is carbon nanomaterial, referred to as diamond carbon cage acid sodium crystal.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, described that product is concentrated in water simultaneously
It crystallizes at normal temperature, dissolves product for water is slowly added into product, room temperature to crystallization.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, described that diamond carbon cage acid sodium is brilliant
Body is heated to color and fades to grey black, and grey black solids is the nano material of diamond carbon basket structure.
A kind of nano material of diamond carbon basket structure, the nano material of the diamond carbon basket structure is by ten carbon atom structures
At diamond carbon basket structure, the diamond carbon basket structure is, by the carbon atom on eight vertex in square body diamond structure cell
It deletes, remaining ten carbon atoms constitute diamond carbon basket structure.
A kind of preparation method of copper-iron alloy, includes the following steps：
（1）The volume ratio of the nano material of copper nanoparticle, nanometer iron powder and diamond carbon basket structure is pressed 1:1:1 is uniformly mixed,
The mouldability and plasticity to improve powder are usually added into the plasticizer such as machine oil, rubber or paraffin afterwards；
（2）Compression moulding：Powder is compacted in cylindrical cavities, is pressed into column；
（3）Sintering：It is sintered in the high temperature furnace or vacuum drying oven of protective atmosphere；
（4）Detection：Sintered copper-iron alloy is splitted, section color is uniform.
Although the present invention in higher temperature environment, without the hazardous gas of hydrogen one kind, danger would not be generated,
It is good for since NaOH reconfigures C-C in molten condition, has the condition of industrialized production.
Detailed description of the invention
The carbon atom on eight vertex in Fig. 1 pros body diamond structure cell is deleted, and remaining ten carbon atoms constitute diamond
Carbon basket structure.
Specific embodiment
The invention is realized in this way：NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, by following methods
It realizes：In 600 DEG C -900 DEG C of inert gas environment, carbon material is mixed in the molten state with NaOH, in molten condition
Under mixed process in the C-C in carbon material is reconfigured, formed carbon nanomaterial.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, and the carbon material is 8-12 moles
The carbon material of aromatic ring structure mixes in the molten state with 6-10 moles of NaOH, and temperature range is 700 DEG C -800 DEG C.Specification
Add：The proportion of two kinds of components and matching not in strict accordance with the carbon material of 8-12 moles of aromatic ring structure and 6-10 moles of NaOH
Than proportion only has indicative function, because reconstruct not fully carries out according to the proportion.Selection aromatic ring structure carbon material be because
It is the material that plant fiber carbonizes that NaOH to find once in a while, which reconfigures the strong carbon nanomaterial for preparing of C-C, and plant fiber exists
The material of 600 DEG C of -900 DEG C of charings is mainly the carbon material of aromatic ring structure, so that NaOH reconfigures the carbon material of aromatic ring structure
The strong probability for preparing carbon nanomaterial of C-C substantially increases.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, and the carbon material is 8-12 moles
Plant fiber charing material mixed in the molten state with 6-10 moles of NaOH, temperature range be 700 DEG C -800 DEG C.It says
Bright book adds：The proportion of two kinds of components and not in strict accordance with the carbon material of 8-12 moles of aromatic ring structure with 6-10 moles of NaOH's
Proportion, secondary proportion only have indicative function.The material of selection plant fiber charing is because of the NaOH found once in a while again structure
Making the strong carbon nanomaterial for preparing of C-C is the material that plant fiber carbonizes.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, after the plant fiber charing
Material is coal dust.Specification adds：The main component of coal is exactly the carbon material of aromatic ring structure.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, after the plant fiber charing
Material is solid carbonaceous material of the plant fiber after 700 DEG C of -800 DEG C of pyrolysis.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, after the plant fiber charing
Material is solid carbonaceous material of the plant fiber after 700 DEG C of -800 DEG C of pyrolysis, is pyrolyzed as further in 700 DEG C -800 DEG C of inertia
In gaseous environment, dry papermaking wood pulp is sprayed into, papermaking wood pulp is pyrolyzed, the solid carbonaceous material after pyrolysis falls into molten condition
The solid carbonaceous material for being pyrolyzed the NaOH of molten condition with papermaking wood pulp mixes.The yield of carbon nanomaterial in this way is higher
It is some.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, and the carbon material and NaOH are and iron
It is carried out in the environment of atomic contacts.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, and the carbon material and NaOH are and iron
It carries out in the environment of atomic contacts, is mixed in iron container for the NaOH of molten condition with carbon material；Product is concentrated in into water
And crystallize at normal temperature, collect the crystal that crystalline solid is carbon nanomaterial, referred to as diamond carbon cage acid sodium crystal.It chances on
This material is exactly to complete under conditions of melting mixing in iron pan；It is also fine that iron powder was added later.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, described that diamond carbon cage acid sodium is brilliant
Body is heated to color and fades to grey black, and grey black solids is the nano material of diamond carbon basket structure.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, and the carbon material and NaOH are and iron
It carries out in the environment of atomic contacts, is mixed for the NaOH of molten condition with addition iron powder in carbon material mixture；Product is dense
It shrinks in water and crystallizes at normal temperature, collect the crystal that crystalline solid is carbon nanomaterial, referred to as diamond carbon cage acid sodium crystal.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, described that product is concentrated in water simultaneously
It crystallizes at normal temperature, dissolves product for water is slowly added into product, room temperature to crystallization.Here water is slowly added into
Product dissolves product, and water, which is preferably slowly added into product, has been completely dissolved product just；But add water
Also unimportant, the time for only crystallizing precipitation is a little longer；Room temperature to crystallization, that is, liquid is evaporated substantially, but
It is to deposit liquid to nor affect on.
The NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, described that diamond carbon cage acid sodium is brilliant
Body is heated to color at 750 °C and fades to grey black, and grey black solids is the nano material of diamond carbon basket structure.
A kind of nano material of diamond carbon basket structure, if the nano material of Fig. 1 diamond carbon basket structure is by ten carbon
Atomic building diamond carbon basket structure, the diamond carbon basket structure are, by eight vertex in square body diamond structure cell 1
Carbon atom is deleted, and remaining ten carbon atoms constitute diamond carbon basket structure 2.
A kind of preparation method of copper-iron alloy, includes the following steps：
（1）The volume ratio of the nano material of copper nanoparticle, nanometer iron powder and diamond carbon basket structure is pressed 1:1:1 is uniformly mixed,
The mouldability and plasticity to improve powder are usually added into the plasticizer such as machine oil, rubber or paraffin afterwards；
（2）Compression moulding：Powder is compacted in cylindrical cavities, is pressed into column；
（3）Sintering：It is sintered in the high temperature furnace or vacuum drying oven of protective atmosphere；
（4）Detection：Sintered copper-iron alloy is splitted, section color is uniform, and display uniformly mixes copper and iron.
Claims (14)
1.NaOH reconfigures the strong new application for preparing carbon nanomaterial of C-C, is realized by following methods：
In 600 DEG C -900 DEG C of inert gas environment, carbon material is mixed in the molten state with NaOH, in the molten state
Mixed process in the C-C in carbon material is reconfigured, formed carbon nanomaterial.
2. NaOH as described in claim 1 reconfigures the strong new application for preparing carbon nanomaterial of C-C, it is characterised in that：Institute
It states the carbon material of aromatic ring structure that carbon material is 8-12 moles to mix in the molten state with 6-10 moles of NaOH, temperature range
It is 700 DEG C -800 DEG C, specification adds：The proportion of two kinds of components and not in strict accordance with the carbon material of 8-12 moles of aromatic ring structure with
The proportion of 6-10 moles of NaOH, proportion only have indicative function, because reconstruct not fully carries out according to the proportion, selection virtue
The carbon material of ring structure is that the strong carbon nanomaterial for preparing is plant fiber charing because the NaOH found once in a while reconfigures C-C
Material, and the material that plant fiber is carbonized at 600 DEG C -900 DEG C is mainly the carbon material of aromatic ring structure, so that NaOH is reconfigured
The strong probability for preparing carbon nanomaterial of the carbon material C-C of aromatic ring structure substantially increases.
3. NaOH as described in claim 1 reconfigures the strong new application for preparing carbon nanomaterial of C-C, it is characterised in that：Institute
The carbon material stated is that the material of 8-12 moles of plant fiber charing mixes in the molten state with 6-10 moles of NaOH, temperature
Range is 700 DEG C -800 DEG C, and specification adds：The carbon materials of the proportion of two kinds of components and the aromatic ring structure not in strict accordance with 8-12 moles
The proportion of material and 6-10 moles of NaOH, secondary proportion only have indicative function, the material for selecting plant fiber charing be because
It is the material that plant fiber carbonizes that the NaOH found once in a while, which reconfigures the strong carbon nanomaterial for preparing of C-C,.
4. NaOH as claimed in claim 2 reconfigures the strong new application for preparing carbon nanomaterial of C-C, it is characterised in that：Institute
Material after the plant fiber charing stated is coal dust, and specification adds：The main component of coal is exactly the carbon material of aromatic ring structure.
5. NaOH as claimed in claim 3 reconfigures the strong new application for preparing carbon nanomaterial of C-C, it is characterised in that：Institute
Material after the plant fiber charing stated is solid carbonaceous material of the plant fiber after 700 DEG C of -800 DEG C of pyrolysis.
6. NaOH as claimed in claim 5 reconfigures the strong new application for preparing carbon nanomaterial of C-C, it is characterised in that：Institute
Material after the plant fiber charing stated is solid carbonaceous material of the plant fiber after 700 DEG C of -800 DEG C of pyrolysis, is pyrolyzed as into one
Step sprays into dry papermaking wood pulp, papermaking wood pulp is pyrolyzed, the solid after pyrolysis in 700 DEG C -800 DEG C of inert gas environment
Carbon material falls into the NaOH of molten condition the solid carbonaceous material for being pyrolyzed the NaOH of molten condition with papermaking wood pulp and mixes, in this way
The yield of carbon nanomaterial is some higher.
7. the NaOH as described in claim 1-6 reconfigures the strong new application for preparing carbon nanomaterial of C-C, it is characterised in that：
The carbon material with NaOH is carried out in the environment of contacting with iron atom.
8. NaOH as claimed in claim 7 reconfigures the strong new application for preparing carbon nanomaterial of C-C, it is characterised in that：Institute
Carbon material, which is stated, with NaOH is carried out in the environment of contacting with iron atom, is that the NaOH of molten condition and carbon material mix in iron container
It closes；Product is concentrated in into water and is crystallized at normal temperature, the crystal that crystalline solid is carbon nanomaterial, referred to as diamond carbon are collected
Cage acid sodium crystal, chancing on this material is exactly to complete under conditions of melting mixing in iron pan；It is later that iron powder is added also very
It is good.
9. NaOH as claimed in claim 8 reconfigures the strong new application for preparing carbon nanomaterial of C-C, it is characterised in that：Institute
It states and diamond carbon cage acid sodium crystal is heated to color fades to grey black, grey black solids is receiving for diamond carbon basket structure
Rice material.
10. NaOH as claimed in claim 7 reconfigures the strong new application for preparing carbon nanomaterial of C-C, it is characterised in that：Institute
Carbon material, which is stated, with NaOH is carried out in the environment of contacting with iron atom, to be added in the NaOH and carbon material mixture of molten condition
Iron powder mixing；Product is concentrated in into water and is crystallized at normal temperature, the crystal that crystalline solid is carbon nanomaterial is collected, it is referred to as golden
Hard rock carbon cage acid sodium crystal.
11. NaOH as claimed in claim 10 reconfigures the strong new application for preparing carbon nanomaterial of C-C, it is characterised in that：
It is described that product is concentrated in into water and is crystallized at normal temperature, dissolve product for water is slowly added into product, room temperature
To crystallization.
12. NaOH as claimed in claim 11 reconfigures the strong new application for preparing carbon nanomaterial of C-C, it is characterised in that：
Described diamond carbon cage acid sodium crystal is heated to color to fade to grey black, grey black solids is diamond carbon basket structure
Nano material.
13. a kind of nano material of diamond carbon basket structure, the nano material of the diamond carbon basket structure is by ten carbon atom structures
At diamond carbon basket structure, the diamond carbon basket structure is, by the carbon atom on eight vertex in square body diamond structure cell
It deletes, remaining ten carbon atoms constitute diamond carbon basket structure.
14. a kind of preparation method of copper-iron alloy, includes the following steps：
（1）The volume ratio of the nano material of copper nanoparticle, nanometer iron powder and diamond carbon basket structure is pressed 1:1:1 is uniformly mixed,
The mouldability and plasticity to improve powder are usually added into the plasticizer such as machine oil, rubber or paraffin afterwards；
（2）Compression moulding：Powder is compacted in cylindrical cavities, is pressed into column；
（3）Sintering：It is sintered in the high temperature furnace or vacuum drying oven of protective atmosphere；
（4）Detection：Sintered copper-iron alloy is splitted, section color is uniform.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144190A (en) * | 1995-08-30 | 1997-03-05 | 方宝贤 | Method and apparatus for production of fullerences from coal |
| WO2016184355A1 (en) * | 2015-05-19 | 2016-11-24 | 张雨虹 | Method for preparing graphene using coal as raw material |
-
2017
- 2017-05-27 CN CN201710393690.5A patent/CN108928810A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144190A (en) * | 1995-08-30 | 1997-03-05 | 方宝贤 | Method and apparatus for production of fullerences from coal |
| WO2016184355A1 (en) * | 2015-05-19 | 2016-11-24 | 张雨虹 | Method for preparing graphene using coal as raw material |
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