KR20140050503A - Defective carbon materials and fabrication method therof - Google Patents
Defective carbon materials and fabrication method therof Download PDFInfo
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- KR20140050503A KR20140050503A KR1020130001560A KR20130001560A KR20140050503A KR 20140050503 A KR20140050503 A KR 20140050503A KR 1020130001560 A KR1020130001560 A KR 1020130001560A KR 20130001560 A KR20130001560 A KR 20130001560A KR 20140050503 A KR20140050503 A KR 20140050503A
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- carbon material
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- carbon
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 230000002950 deficient Effects 0.000 title description 2
- 230000007547 defect Effects 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 12
- 150000004706 metal oxides Chemical class 0.000 abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 43
- 229910021393 carbon nanotube Inorganic materials 0.000 description 21
- 239000002041 carbon nanotube Substances 0.000 description 21
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 150000002736 metal compounds Chemical class 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- JYEZJKNOMNWVLJ-UHFFFAOYSA-N cobalt tetrahydrate Chemical compound O.O.O.O.[Co] JYEZJKNOMNWVLJ-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- KJIYBINEQTYQCF-UHFFFAOYSA-N cobalt;hexahydrate Chemical compound O.O.O.O.O.O.[Co] KJIYBINEQTYQCF-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 239000002180 crystalline carbon material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- NSVFPFUROXFZJS-UHFFFAOYSA-N nickel;hexahydrate Chemical compound O.O.O.O.O.O.[Ni] NSVFPFUROXFZJS-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0061—Methods for manipulating nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
Abstract
Contacting a compound containing a metal with a carbon material; and introducing a defect having chemical activity into the carbon material by heating the sample obtained by the contact in air. do. The present invention is not limited to one material but can introduce defects in all carbon materials. In particular, in the technical aspect, the present invention does not require a pretreatment process, and increases the specific surface area by introducing defects in carbon materials without using metal oxides, and activates the surface thereof to activate fuel cells, lithium ion batteries, semiconductors, The invention has the significance of facilitating applications in various fields such as gas sensors, catalysts, medicine, and the like.
Description
The present invention relates to a carbon material, and more particularly, to a technique for introducing a defect into a carbon material to increase the specific surface area and to activate the surface thereof.
Carbon materials such as graphite, graphene, and carbon nanotubes, due to their excellent mechanical and chemical properties, are found in many areas of the industry such as fuel cells, lithium ion batteries, semiconductors, gas sensors, and catalysts. It is a substance used throughout.
The excellent mechanical properties of the carbon materials listed above are due to the properties of the surface with little defects. Thus, the surface of the materials is physicochemically inactive unless otherwise treated. This is an obstacle to the above listed materials when applied to industrial applications, and in order to solve this problem, heat treatment for heating the materials to a high temperature in a gas atmosphere of oxygen, ozone and carbon dioxide, sulfuric acid, nitric acid, hydrochloric acid or their Methods such as acid treatment are used to boil mixed acids to activate the surface of the material. However, the treatment method activates the surface and increases the specific surface area, but the inherent crystallinity of the tango materials deteriorates after treatment, which limits the inherent strength.
The result of overcoming this limitation is Pub. No .: US 2011/0206932 A1, which is a technique in which a metal oxide is formed on the surface of a carbon nanotube and heated to remove some of the carbon in the carbon nanotube, thereby introducing only a part of defects while maintaining inherent crystallinity. As a result, the specific surface area is increased and the surface is activated. However, this technology is limited to carbon nanotubes, and in order to introduce defects, it is necessary to form metal oxides on the surface of carbon nanotubes. This process is expensive because of the high temperature and inert gas atmosphere, and due to the long process technology, it takes a long time to produce. In addition, the embodiment includes a pretreatment process for purifying with an acid before forming a metal oxide on the surface of the carbon nanotubes, which has technical problems in terms of cost and stability of operation.
Preceding Document Number: Pub. No .: US 2011/0206932 A1
The difference from the present invention is a technique limited to carbon nanotubes in the case of the prior art, and also introduces a defect and is more complicated than the present invention.
That is, in the prior art, carbon nanotubes are subjected to a pretreatment and purification process using an acid, an impregnation of a metal salt on the surface of the carbon nanotubes, and then heated under an argon (Ar) atmosphere to the surface of the carbon nanotubes. Form nanoscale metal oxides. Thereafter, the sample is heated in air to introduce defects into the carbon nanotubes through reaction with the metal oxide formed on the surface of the carbon nanotubes and the carbon present on the surface of the carbon nanotubes.
On the other hand, the present invention is not limited to carbon nanotubes through a simplified process, it is a distinct difference from the prior art that is applied to all carbon materials such as graphite, graphene. The present invention does not undergo a purification process of acid treatment, and the metal-containing compound is contacted with the carbon material through various methods. The carbon material in contact with the metal compound is then directly heated in air to create a direct defect. This does not require a purification process using the acid required prior to metal oxide production, thereby ensuring operational stability and reducing the cost required for the purification process. In addition, since the process of heating using argon gas is unnecessary to make the metal oxide, it has the advantage of economic cost saving effect and suitable for mass production due to process shortening.
In the technical aspect, the present invention is not limited to one specific material, and by using a crystalline and amorphous carbon material, the carbon material is made to be defects without undergoing a purification process using an acid corresponding to a pretreatment and forming a metal oxide. It is an object to increase the surface area and to activate the surface so that it can be used in various applications. In economic terms, the aim is to secure technology that enables cost savings, work stability and mass production through streamlined processes.
In order to achieve the above object, the present invention comprises the steps of contacting a compound containing a metal with a carbon material; and introducing a defect having chemical activity in the carbon material by heating the sample obtained by the contact in air; Provided are a method for producing a carbon material having a defect and a carbon material having a defect produced thereby.
The carbon material includes crystals and amorphous, and is not limited to one material, characterized in that the metal is not limited to any.
The present invention includes a step of contacting a compound including a metal with a carbon material, and introducing a defect into the carbon material.
The method of contacting a compound containing a metal with a carbon material is various and is not limited to any one method. That is, the compound containing the metal may be dissolved to form a solution, and the carbon material may be dispersed in the solution, and then the mixed solution may be contacted by stirring and heating. The carbon material may be transferred onto a substrate, a compound containing a metal may be dissolved to form a solution, and then the solution may be dropped onto the carbon material transferred to the substrate, and then the solution may be dried to be contacted. In addition, after the compound containing the metal and the carbon material is mixed, the two materials may be finely ground and contacted.
The sample obtained by the contact is heated in air at a temperature of 50 ~ 1000 ℃ to introduce defects in the carbon material, increase the specific surface area of the carbon material and at the same time activate the surface of the fuel cell, lithium ion battery, semiconductor, gas It is easy to apply to various fields such as sensor, catalyst, medicine, etc.
Meanwhile, the present invention may further include a purification step of removing impurities from the carbon material into which the defect is introduced. Here, the purification process may not be applied depending on the application purpose.
The present invention is not limited to one material but can introduce defects in all carbon materials. In particular, in the technical aspect, the present invention does not require a pretreatment process, and increases the specific surface area by introducing defects in carbon materials without using metal oxides, and activates the surface thereof to activate fuel cells, lithium ion batteries, semiconductors, The invention has the significance of facilitating applications in various fields such as gas sensors, catalysts, medicine, and the like.
In terms of economics, the present invention does not use a metal oxide formation process to introduce defects into the carbon material, and does not require an acid purification process to form metal oxides. Due to the process, cost reduction and mass production can be expected.
1 is a process chart for introducing crystal defects into a carbon material;
2 is carbon nanotubes in which crystal defects are introduced by an iron compound,
3 is carbon nanotubes in which crystal defects are introduced by cobalt compounds;
4 is a comparison of the specific surface area after the introduction of crystal defects by iron compounds,
5 is graphite in which crystal defects are introduced by cobalt compounds;
6 is graphite in which crystal defects are introduced by a copper compound.
According to the present invention, a compound including a metal is contacted with a surface of a carbon material through various methods, and then the material is heated in air to form defects in the carbon material structure. Here, the carbon material includes crystalline and amorphous, and is not limited to one material, for example, active carbon, carbon black, graphite, graphene, graphite oxide , Graphene oxide, carbon nanotube, etc. may be used as the material. In addition, the contact method of the compound containing a metal and a carbon material is various, and is not limited to any one method.
The present invention is largely divided into three steps: a process of contacting a compound containing a metal with a carbon material, a process of introducing defects into the carbon material, and a refining process (see FIG. 1). It may be.
end. Contacting a carbon-containing compound with a metal
The process of contacting the carbon material and the compound containing the metal may be variously modified depending on the carbon material and its application purpose.
1) Contact method by solution mixing
The method consists of the following three steps, and is a method of roughly dissolving a compound containing a metal in a solvent and then contacting the metal compound and the carbon material by adding a carbon material to the solution. At this time, the solvent may be selected in various ways depending on the characteristics of the compound containing a metal (for example, ethanol, methanol-based alcohol and organic solvent, water, acid solution and base solution, etc.), It is not limited to either solvent.
a) preparing a compound solution containing a metal
The compound containing the metal is dissolved in a suitable solution to dissolve the compound in the solution. At this time, the weight ratio of the metal compound to be used is suitably 0.1 to 90% by weight of the carbon material to be used. The use of small amounts of metal compounds of less than 0.1% by weight can create very small defects (small holes) in the carbon material, but it is very time consuming, while using a large amount of metal compounds of more than 90% by weight, 0.1 to 90% by weight is suitable because there is a problem of creating a too large defect (in the form of a large hole) in a short time.
In addition, the compound containing the metal is not limited to any particular form. Typical examples of cobalt include cobalt tetrahydrate (Co (CH 3 COO) 2 4H 2 O), cobalt carbonate (CoCO 3 ), cobalt chloride (CoCl 2 ), and cobalt nitrate (Co (NO 3). ) 2 ), cobalt hexahydrate (Co (NO 3 ) 2 · 6H 2 O), cobalt sulfate (CoSO 4 ), and when nickel is used, nickel hexahydrate (Ni (NO 3 ) 2 ·) 6H 2 O), hexavalent nickel sulfate (Ni (SO 4 ) 2 · 6H 2 O), nickel carbonate (NiCO 3 ), hexavalent nickel chloride (NiCl 2 · 6H 2 O), tetrahydrate nickel acetate (Ni (CH 3 COO) 2 .4H 2 O), and when copper is used, copper acetate, copper carbonate (Cu 2 (OH) 2 CO 3 ), copper chloride (CuCl 2 ), copper hydroxide (Cu ( OH) 2 ), copper nitrate (Cu (NO 3 ) 2 ), copper sulphate, and when iron is used, ferric nitrate hexahydrate (Fe (NO 3 ) 3 · 9H 2 O), ferrous sulfate (FeSO 4 ), and the like, and the compound containing a metal used in the present invention is not limited to the exemplary compounds listed above.
b) dispersing the carbon material in solution
The carbon material is dispersed in a solution in which the compound containing the metal is present. In this case, a dispersion may be used or an ultrasonic apparatus may be used depending on the solution for dispersion. Preferably, dispersion is performed using an ultrasonic device.
c) a process of contacting a compound containing a carbon material and a metal
The mixed solution in which the carbon material is dispersed is heated with stirring to completely evaporate the solution so that the metal-containing compound contacts the carbon material. At this time, the heating temperature is different depending on the solution, preferably between 30 ~ 200 ℃.
2) Contact Method Using Substrate
This method consists of the following two steps, and is a method of contacting a carbon-containing compound with a carbon-containing compound by dropping a solution containing a metal compound in a carbon material transferred onto a substrate.
a) transfer process of carbon material
The carbon material is transferred onto the substrate through various methods. The transfer process may vary depending on the carbon material and the application purpose, and is preferably transferred using a tape. At this time, the type of substrate is determined according to the application purpose and is not limited to any one type. Preferably a silicon substrate or a glass substrate can be used.
b) dropping solution
After preparing a solution containing a metal compound in the same manner as above, the solution is dropped on the carbon material transferred to the substrate, and the solution is dried. At this time, the drying temperature is preferably 20-100 ℃.
3) Contact method by grinding mixing
This method is a method of contacting a compound containing a carbon material and a metal by mixing the carbon material and a compound containing a metal, and then pulverizing the two materials. The grinding method may vary, and preferably grinding by hand using a mortar and pestle.
I. Defect introduction process
The sample obtained through the above contact method is heated at a temperature of 50 to 1000 ° C. in an air atmosphere to introduce defects into the carbon material. At this time, the heating time is between 1 minute and 24 hours.
All. Purification Process
This step is a step for obtaining a pure carbon material having a defect, and is a step for obtaining a pure carbon material having a defect by removing impurities from the carbon material obtained in the above step using a solution of an acid or acid diluted with water. This process may not be performed depending on the end application.
Hereinafter, with reference to the accompanying drawings will be described a preferred embodiment of the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Example 1
This example shows a method of introducing defects into a carbon material by selecting carbon nanotubes as the carbon material and Fe (NO 3 ) 3 .9H 2 O as the compound containing the metal. Here, the carbon material and the metal compound are brought into contact with each other using a contact method by solution mixing.
1. Dissolve 0.01 ~ 10g of Fe (NO 3 ) 3 · 9H 2 O in 1 ~ 1000ml of ethanol.
2. Add 0.1 ~ 10g carbon nanotubes to the solution and disperse by applying ultrasonic wave for 15 minutes.
3. Heat the solution above at 50-100 ° C. until the solution evaporates completely.
4. The sample is heated at 150-500 ° C. for about 0.5-24 hours in air.
Carbon material implemented as described above will have a defect in the form of pores at the nanoscale level, as shown in Figure 2, the resulting surface is chemically active.
Example 2
This example shows a method of introducing defects into a carbon material by selecting carbon nanotubes as a carbon material and Co (NO 3 ) 2 .6H 2 O as a compound containing a metal. Here, the carbon material and the metal compound are brought into contact with each other using a contact method by solution mixing.
1. Dissolve 0.01 ~ 10g Co (NO 3 ) 2 · 6H 2 O in 1 ~ 1000ml of ethanol.
2. Add 0.1 ~ 10g carbon nanotubes to the solution and disperse by applying ultrasonic wave for 15 minutes.
3. Heat the solution above at 50-100 ° C. until the solution evaporates completely.
4. The sample is heated at 150-500 ° C. for about 0.5-24 hours in air.
5. Purify the sample by stirring into 10-1000 ml of 2 mol sulfuric acid solution.
Carbon material implemented as described above will have a hole-shaped defect at the nanoscale level, as shown in Figure 3, the resulting surface is chemically active. In addition, the specific surface area increases from 432m 2 / g to 580m 2 / g as shown in FIG.
Example 3
This example shows a method of introducing defects into a carbon material by selecting graphite as the carbon material and Co (NO 3 ) 2 .6H 2 O as the compound containing the metal. Here, the carbon material and the metal compound are brought into contact with each other using a substrate contact method.
1. Transfer graphite onto the silicon substrate using tape.
2. Dissolve 0.01 ~ 10g Co (NO 3 ) 2 · 6H 2 O in 1 ~ 1000ml of ethanol.
3. Drop the solution onto the silicon substrate on which the graphite is transferred.
4. The sample is heated at 150-500 ° C. in air for about 0.5-24 hours.
Carbon material implemented as described above will have a hole-shaped defects at the micro-scale level as shown in Figure 5 and nano-sized defects also exist at the same time. The surface thus produced is chemically active.
Example 4
This embodiment shows a method of introducing defects into the carbon material by selecting graphite as the carbon material and Cu (CH 3 COO) 2 as the compound containing the metal. Here, the carbon material and the metal compound are brought into contact with each other using a substrate contact method.
1. Transfer graphite onto the silicon substrate using tape.
2. Dissolve 0.01-10 g of Cu (CH 3 COO) 2 in 1-1000 ml of ethanol.
3. Drop the solution onto the silicon substrate on which the graphite is transferred.
4. The sample is heated at 150-500 ° C. for about 0.5-24 hours in air.
The carbon material carried out as described above has a hole-type defect at the micro-scale level as shown in FIGS. 2 to 6 and nano-scale defects also exist at the same time. The surface thus produced has an increased specific surface area and is chemically active as shown in FIG. 4.
Although the present invention has been described in terms of some preferred embodiments, the scope of the present invention should not be limited thereby but should be modified and improved in accordance with the above-described embodiments.
Claims (9)
Heating the sample obtained by the contact in air to introduce a defect into the carbon material.
And a refining step of removing impurities from the carbon material into which the defects are introduced.
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| KR1020120116849 | 2012-10-19 | ||
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104112854A (en) * | 2014-06-30 | 2014-10-22 | 陕西师范大学 | Preparation method of SnO2 nanocrystal/C sheet composite material with large specific surface area |
| CN110634591A (en) * | 2019-09-29 | 2019-12-31 | 新奥石墨烯技术有限公司 | Conductive paste, preparation method and application thereof, and battery |
| WO2024044310A1 (en) * | 2022-08-24 | 2024-02-29 | Robert Bosch Gmbh | Fuel cell electrode catalyst protective layer forming method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104112854A (en) * | 2014-06-30 | 2014-10-22 | 陕西师范大学 | Preparation method of SnO2 nanocrystal/C sheet composite material with large specific surface area |
| CN110634591A (en) * | 2019-09-29 | 2019-12-31 | 新奥石墨烯技术有限公司 | Conductive paste, preparation method and application thereof, and battery |
| CN110634591B (en) * | 2019-09-29 | 2021-04-16 | 新奥石墨烯技术有限公司 | Conductive paste, preparation method and application thereof, and battery |
| WO2024044310A1 (en) * | 2022-08-24 | 2024-02-29 | Robert Bosch Gmbh | Fuel cell electrode catalyst protective layer forming method |
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