CN104925780A - Preparation method for multilayer flaky carbon material - Google Patents
Preparation method for multilayer flaky carbon material Download PDFInfo
- Publication number
- CN104925780A CN104925780A CN201510093776.7A CN201510093776A CN104925780A CN 104925780 A CN104925780 A CN 104925780A CN 201510093776 A CN201510093776 A CN 201510093776A CN 104925780 A CN104925780 A CN 104925780A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- reaction
- preparation
- catalyst precursor
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 238000003837 high-temperature calcination Methods 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 7
- 238000011946 reduction process Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000007769 metal material Substances 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
Abstract
The invention relates to a preparation method for a multilayer flaky carbon material, belonging to the field of preparation of inorganic non-metallic materials. According to the invention, cobaltosic oxide with a flaky structure is used as a catalyst precursor; hydrogen is used as the catalyst precursor for reduction treatment of gas through a chemical vapor deposition method; and acetylene gas is used as carbon source gas, so the carbon material with a multilayer flaky structure is prepared. The invention has the following advantages: preparation process of the multilayer flaky carbon material is simple in process and easy to operate; production scale is easy to expand; and product repeatability is high.
Description
Technical field
The present invention relates to a kind of preparation method of multilayer chip carbon material, belong to ceramic preparation field.
Background technology
Carbon, form one of important element of all things on earth as occurring in nature, the carbon material be made up of it causes research interest and the concern of vast researcher because of its distinctive structure and properties.Carbon material possesses the characteristic of many excellences, such as, good electroconductibility, thermal conductivity, acid resistance, alkali resistance and high strength, low density etc., make it all be widely applied in aerospace, chemical, energy machinery, the biomedicine even various fields such as military heavy industry.
As everyone knows, carbon has multiple allotropic substance, comprising graphite, diamond, decolorizing carbon that people know already, and the new carbon such as the carbon nanotube found along with scientific-technical progress afterwards, carbon fiber, Graphene.Although be the pure substance of carbon composition, due to the difference in weave construction, above-mentioned carbon material shows greatest differences in performance properties.Such as, graphite is the good conductor of electricity, and diamond shows as the isolator of electricity; Graphite is the material that nature is the softest, and adamantine hardness is very high.As can be seen here, by carrying out on purpose active designs and effectively realizing to the structure and morphology of carbon material and existence, and then can change or improve character and the performance of carbon material aspect, as the size, density, specific surface area etc. of carbon material.
Under same volume condition, multilayer chip structure effectively can improve the specific surface area of material, this point meets the requirement of the Application Areas such as ultracapacitor, lithium ion battery to electrode materials especially, because high-specific surface area can improve speed of reaction and the efficiency of electrode.When the electrode utilizing multilayer chip structural carbon material to prepare, electrolytic solution can enter into the space between sheet and sheet and electrode reaction occurs, efficiently and effectively increases reaction area, and the permutoid reaction area of ion or electronics effectively improves, the ability of high current charge-discharge that made it possess.
Chemical Vapor deposition process is that a kind of technique is simple to operation, industrial scale easily expands the carbon material high with product repetition rate and commonly uses preparation method, and its main technologic parameters comprises temperature of reaction, reaction times, temperature rise rate, carbon source kind, type carrier gases and catalyst type and form.By effectively controlling processing parameter ground, can prepare the carbon material with specific morphology and state, the method is widely used in carbon nanotube, the carbon fiber even preparation field of the carbon material such as Graphene.
In this application, have employed there is flaky nanometer structure tricobalt tetroxide as catalyst precursor, according to its physicochemical property, choose and set temperature of reaction and the reaction times of chemical Vapor deposition process, under the prerequisite not destroying its laminate structure, prepare the carbon material with multilayer chip structure.
Summary of the invention
1, the present invention relates to a kind of preparation method of multilayer chip carbon material, it is characterized in that in the method, first hydrothermal method and subsequent high temperature calcining is utilized to prepare tricobalt tetroxide catalyst precursor, then chemical Vapor deposition process is passed through, hydrogen is as catalyst precursor reduction treatment gas, and acetylene gas has prepared the carbon material with multilayer chip structure as carbon source.In this preparation process, simple to operate, reaction conditions is gentle and easy to control, comprises following key step:
(1) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO is utilized
3)
26H
2and urea (CO (NH O)
2)
2), prepared the intermediate product with laminated structure by hydrothermal method, then high-temperature calcination is carried out to it, obtain the tricobalt tetroxide catalyst precursor with sheet structure;
(2) get appropriate tricobalt tetroxide catalyst precursor and be placed in porcelain boat, and put it in the reaction tubes of tubular react furnace;
(3) reaction tubes is vacuumized, then according to the temperature rise rate of setting, reaction tubes is risen to temperature of reaction by room temperature;
(4) hydrogen is passed into reaction tubes to normal atmosphere, tricobalt tetroxide catalyst precursor is carried out to the high temperature reduction process of certain hour;
(5) after hydrogen reducing process terminates, hydrogen is taken out, then pass into carbon-source gas acetylene to normal atmosphere, and keep certain reaction times;
(6) after reaction terminates, the residual gas in reaction tubes is taken out, and keeps vacuum, after naturally cooling to room temperature, collect the product in porcelain boat.
2, the preparation method of a kind of multilayer chip carbon material according to claim 1, the temperature rise rate setting range that it is characterized in that in step (3) is 3 DEG C/min ~ 10 DEG C/min.
3, the preparation method of a kind of multilayer chip carbon material according to claim 1 and 2, is characterized in that the range of reaction temperature of setting in step (3) is 260 DEG C ~ 550 DEG C.
The preparation method of a kind of multilayer chip carbon material 4, according to claim 1,2 or 3, is characterized in that, in step (4), hydrogen reducing treatment time scope is 20min ~ 40min.
The preparation method of a kind of multilayer chip carbon material 5, according to claim 1,2,3 or 4, is characterized in that the reaction times in step (5) is 20min ~ 60min.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope secondary electron photo of multilayer chip carbon material, clearly can observe the sheet structure of carbon material from figure, and its thickness is 150nm ~ 300nm.
Fig. 2 be the scanning electron microscope backscattered electron composition of multilayer chip carbon material as photo, wherein brighter in figure part is the position at catalyst metal cobalt granule place, generally within the central position of sheet carbon material.
Fig. 3 is the XRD spectra of tricobalt tetroxide catalyzer.According to the analysis to spectrogram, can determine that catalyst precursor is tricobalt tetroxide (JCPDS 43-1003), there is no the appearance of other diffraction peaks, illustrate there is no other impurity.
Fig. 4 is the XRD spectra of multilayer chip carbon material.Can be known by figure, the catalyzer in multilayer chip carbon material is that cobalt metal (JCPDS 05-0727), the 2 θ diffuse peaks between 20 ° ~ 30 ° comes from the multilayer chip carbon material with amorphous structure.
Embodiment
Embodiment one:
(1) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO is utilized
3)
26H
2and urea (CO (NH O)
2)
2), prepared the intermediate product with laminated structure by hydrothermal method, then high-temperature calcination is carried out to it, obtain the tricobalt tetroxide catalyst precursor with sheet structure;
(2) get appropriate tricobalt tetroxide catalyst precursor and be placed in porcelain boat, and put it in the reaction tubes of tubular react furnace;
(3) vacuumize reaction tubes, then setting temperature rise rate is 4 DEG C/min, and reaction tubes is risen to temperature of reaction 300 DEG C by room temperature;
(4) hydrogen is passed into reaction tubes to normal atmosphere, tricobalt tetroxide catalyst precursor is carried out to the high temperature reduction process of 20min;
(5) after hydrogen reducing process terminates, hydrogen is taken out, then pass into carbon-source gas acetylene to normal atmosphere, and keep the reaction times of 45min;
(6) after reaction terminates, the residual gas in reaction tubes is taken out, and keeps vacuum, after naturally cooling to room temperature, collect the product in porcelain boat.
Embodiment two:
(1) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO is utilized
3)
26H
2and urea (CO (NH O)
2)
2), prepared the intermediate product with laminated structure by hydrothermal method, then high-temperature calcination is carried out to it, obtain the tricobalt tetroxide catalyst precursor with sheet structure;
(2) get appropriate tricobalt tetroxide catalyst precursor and be placed in porcelain boat, and put it in the reaction tubes of tubular react furnace;
(3) vacuumize reaction tubes, then setting temperature rise rate is 4 DEG C/min, and reaction tubes is risen to temperature of reaction 300 DEG C by room temperature;
(4) hydrogen is passed into reaction tubes to normal atmosphere, tricobalt tetroxide catalyst precursor is carried out to the high temperature reduction process of 30min;
(5) after hydrogen reducing process terminates, hydrogen is taken out, then pass into carbon-source gas acetylene to normal atmosphere, and keep the reaction times of 30min;
(6) after reaction terminates, the residual gas in reaction tubes is taken out, and keeps vacuum, after naturally cooling to room temperature, collect the product in porcelain boat.
Embodiment three:
(1) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO is utilized
3)
26H
2and urea (CO (NH O)
2)
2), prepared the intermediate product with laminated structure by hydrothermal method, then high-temperature calcination is carried out to it, obtain the tricobalt tetroxide catalyst precursor with sheet structure;
(2) get appropriate tricobalt tetroxide catalyst precursor and be placed in porcelain boat, and put it in the reaction tubes of tubular react furnace;
(3) vacuumize reaction tubes, then setting temperature rise rate is 5 DEG C/min, and reaction tubes is risen to temperature of reaction 350 DEG C by room temperature;
(4) hydrogen is passed into reaction tubes to normal atmosphere, tricobalt tetroxide catalyst precursor is carried out to the high temperature reduction process of 30min;
(5) after hydrogen reducing process terminates, hydrogen is taken out, then pass into carbon-source gas acetylene to normal atmosphere, and keep the reaction times of 30min;
(6) after reaction terminates, the residual gas in reaction tubes is taken out, and keeps vacuum, after naturally cooling to room temperature, collect the product in porcelain boat.
Embodiment four:
(1) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO is utilized
3)
26H
2and urea (CO (NH O)
2)
2), prepared the intermediate product with laminated structure by hydrothermal method, then high-temperature calcination is carried out to it, obtain the tricobalt tetroxide catalyst precursor with sheet structure;
(2) get appropriate tricobalt tetroxide catalyst precursor and be placed in porcelain boat, and put it in the reaction tubes of tubular react furnace;
(3) vacuumize reaction tubes, then setting temperature rise rate is 5 DEG C/min, and reaction tubes is risen to temperature of reaction 350 DEG C by room temperature;
(4) hydrogen is passed into reaction tubes to normal atmosphere, tricobalt tetroxide catalyst precursor is carried out to the high temperature reduction process of 25min;
(5) after hydrogen reducing process terminates, hydrogen is taken out, then pass into carbon-source gas acetylene to normal atmosphere, and keep the reaction times of 25min;
(6) after reaction terminates, the residual gas in reaction tubes is taken out, and keeps vacuum, after naturally cooling to room temperature, collect the product in porcelain boat.
Embodiment five:
(1) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO is utilized
3)
26H
2and urea (CO (NH O)
2)
2), prepared the intermediate product with laminated structure by hydrothermal method, then high-temperature calcination is carried out to it, obtain the tricobalt tetroxide catalyst precursor with sheet structure;
(2) get appropriate tricobalt tetroxide catalyst precursor and be placed in porcelain boat, and put it in the reaction tubes of tubular react furnace;
(3) vacuumize reaction tubes, then setting temperature rise rate is 6 DEG C/min, and reaction tubes is risen to temperature of reaction 380 DEG C by room temperature;
(4) hydrogen is passed into reaction tubes to normal atmosphere, tricobalt tetroxide catalyst precursor is carried out to the high temperature reduction process of 20min;
(5) after hydrogen reducing process terminates, hydrogen is taken out, then pass into carbon-source gas acetylene to normal atmosphere, and keep the reaction times of 20min;
(6) after reaction terminates, the residual gas in reaction tubes is taken out, and keeps vacuum, after naturally cooling to room temperature, collect the product in porcelain boat.
Claims (5)
1. the present invention relates to a kind of preparation method of multilayer chip carbon material, it is characterized in that in the method, first hydrothermal method and subsequent high temperature calcining is utilized to prepare tricobalt tetroxide catalyst precursor, then chemical Vapor deposition process is passed through, hydrogen is as catalyst precursor reduction treatment gas, and acetylene gas has prepared the carbon material with multilayer chip structure as carbon source.In this preparation process, simple to operate, reaction conditions is gentle and easy to control, comprises following key step:
(1) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO is utilized
3)
26H
2and urea (CO (NH O)
2)
2), prepared the intermediate product with laminated structure by hydrothermal method, then high-temperature calcination is carried out to it, obtain the tricobalt tetroxide catalyst precursor with sheet structure;
(2) get appropriate tricobalt tetroxide catalyst precursor and be placed in porcelain boat, and put it in the reaction tubes of tubular react furnace;
(3) reaction tubes is vacuumized, then according to the temperature rise rate of setting, reaction tubes is risen to temperature of reaction by room temperature;
(4) hydrogen is passed into reaction tubes to normal atmosphere, tricobalt tetroxide catalyst precursor is carried out to the high temperature reduction process of certain hour;
(5) after hydrogen reducing process terminates, hydrogen is taken out, then pass into carbon-source gas acetylene to normal atmosphere, and keep certain reaction times;
(6) after reaction terminates, the residual gas in reaction tubes is taken out, and keeps vacuum, after naturally cooling to room temperature, collect the product in porcelain boat.
2. the preparation method of a kind of multilayer chip carbon material according to claim 1, the temperature rise rate setting range that it is characterized in that in step (3) is 3 DEG C/min ~ 10 DEG C/min.
3. the preparation method of a kind of multilayer chip carbon material according to claim 1 and 2, is characterized in that the range of reaction temperature of setting in step (3) is 260 DEG C ~ 550 DEG C.
4. the preparation method of a kind of multilayer chip carbon material according to claim 1,2 or 3, is characterized in that, in step (4), hydrogen reducing treatment time scope is 20min ~ 40min.
5. the preparation method of a kind of multilayer chip carbon material according to claim 1,2,3 or 4, is characterized in that the reaction times in step (5) is 20min ~ 60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510093776.7A CN104925780B (en) | 2015-03-01 | 2015-03-01 | A kind of preparation method of multilayer chip carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510093776.7A CN104925780B (en) | 2015-03-01 | 2015-03-01 | A kind of preparation method of multilayer chip carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104925780A true CN104925780A (en) | 2015-09-23 |
| CN104925780B CN104925780B (en) | 2019-04-12 |
Family
ID=54113254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510093776.7A Expired - Fee Related CN104925780B (en) | 2015-03-01 | 2015-03-01 | A kind of preparation method of multilayer chip carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104925780B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094559A (en) * | 2013-01-31 | 2013-05-08 | 湘潭大学 | Co3O4/C lithium ion battery cathode material and preparation method thereof |
| CN103117388A (en) * | 2012-11-21 | 2013-05-22 | 西安银泰新能源材料科技有限公司 | Carbon-coated ferroferric oxide and preparation method and application of carbon-coated ferroferric oxide in lithium battery |
| CN103553149A (en) * | 2013-09-15 | 2014-02-05 | 青岛科技大学 | Method for preparing cobaltosic oxide of nanometer level lamellar structure |
| CN103764554A (en) * | 2011-09-30 | 2014-04-30 | 三菱综合材料株式会社 | Carbon nanofibers encapsulting metal cobalt, and production method therefor |
-
2015
- 2015-03-01 CN CN201510093776.7A patent/CN104925780B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103764554A (en) * | 2011-09-30 | 2014-04-30 | 三菱综合材料株式会社 | Carbon nanofibers encapsulting metal cobalt, and production method therefor |
| CN103117388A (en) * | 2012-11-21 | 2013-05-22 | 西安银泰新能源材料科技有限公司 | Carbon-coated ferroferric oxide and preparation method and application of carbon-coated ferroferric oxide in lithium battery |
| CN103094559A (en) * | 2013-01-31 | 2013-05-08 | 湘潭大学 | Co3O4/C lithium ion battery cathode material and preparation method thereof |
| CN103553149A (en) * | 2013-09-15 | 2014-02-05 | 青岛科技大学 | Method for preparing cobaltosic oxide of nanometer level lamellar structure |
Non-Patent Citations (3)
| Title |
|---|
| JI FENG ET AL.: "Reduction and reconstruction of Co3O4 nanocubes upon carbon deposition", 《J.PHYS.CHEM.B》 * |
| QIAN ZHANG ET AL.: "A simple method to synthesize carbon nanofibers with a parallel growth mode and their capacitive properties", 《MATERIALS RESEARCH EXPRESS》 * |
| SHIBO ZHOU ET AL.: "Synthesis of carbon-coated Co3O4 composite with dendrite-like morphology and its electrochemical performance for lithium-ion batteries", 《J NANOPART RES》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104925780B (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shuck et al. | Effect of Ti3AlC2 MAX phase on structure and properties of resultant Ti3C2T x MXene | |
| Li et al. | Thermal stability of two-dimensional Ti2C nanosheets | |
| Kim et al. | Etching mechanism of monoatomic aluminum layers during MXene synthesis | |
| Guo et al. | Synthesis of two-dimensional carbide Mo2CTx MXene by hydrothermal etching with fluorides and its thermal stability | |
| Yu et al. | Shape-controlled syntheses of Co3O4 nanowires arrays with excellent catalytic performances upon ammonium perchlorate decomposition | |
| KR101801789B1 (en) | Porous carbon materials and methods of manufacturing the same | |
| CN106220180A (en) | A kind of preparation method of two dimensional crystal MXene nano material | |
| CN102757036B (en) | Preparation method of porous graphene | |
| Li et al. | Ambient electrocatalytic N 2 reduction to NH 3 by metal fluorides | |
| CN104944392B (en) | A kind of method that magnanimity prepares graphite phase carbon nitride nanometer sheet | |
| CN106185896B (en) | The preparation method of three-dimensional grapheme and its composite material | |
| Ding et al. | Properties, preparation, and application of tungsten disulfide: A review | |
| Rao et al. | Inorganic graphene analogs | |
| CN102139873A (en) | Method for preparing graphene material by microwave irradiation in vacuum or inert gas environment | |
| Salavati-Niasari et al. | Controlled synthesis of spherical α-Ni (OH) 2 hierarchical nanostructures via a simple hydrothermal process and their conversion to NiO | |
| CN105016331B (en) | Synthetic method of graphene microchip-diamond compound | |
| CN105621406A (en) | Nitrogen-doped porous graphite and preparation method thereof | |
| CN102180462A (en) | Method for preparing modified graphene material in controlled atmosphere environment by microwave irradiation | |
| Sun et al. | Facile synthesis of two-dimensional (2D) nanoporous NiO nanosheets from metal–organic frameworks with superior capacitive properties | |
| Wang et al. | Molten salt synthesis of carbon-doped boron nitride nanosheets with enhanced adsorption performance | |
| De et al. | From 0D to 3D MXenes: their diverse syntheses, morphologies and applications | |
| CN104150470A (en) | Metal-solution reduction method for preparing graphene | |
| Dang et al. | Hydrothermal growth and hydrogen selective sensing of nickel oxide nanowires | |
| Li et al. | Two-dimensional transition metal MXene-based gas sensors: A review | |
| Shi et al. | NiO nanotubes assembled in pores of porous anodic alumina and their optical absorption properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190412 Termination date: 20210301 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |