CN103395773A - Nano carbon hollow sphere and preparation method thereof - Google Patents
Nano carbon hollow sphere and preparation method thereof Download PDFInfo
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- CN103395773A CN103395773A CN2013103467406A CN201310346740A CN103395773A CN 103395773 A CN103395773 A CN 103395773A CN 2013103467406 A CN2013103467406 A CN 2013103467406A CN 201310346740 A CN201310346740 A CN 201310346740A CN 103395773 A CN103395773 A CN 103395773A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910021392 nanocarbon Inorganic materials 0.000 title abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 55
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 36
- 239000006230 acetylene black Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 241000872198 Serjania polyphylla Species 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011796 hollow space material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Abstract
The invention discloses a nano carbon hollow sphere and a preparation method thereof. The preparation method comprises the following steps: suspending acetylene black above the level of a nitric acid solution in a closed reaction kettle, heating the reaction kettle, and performing oxidation reaction on the acetylene black with the generated nitric acid vapor. The average inner diameter of the prepared nano carbon hollow sphere is 20-30nm, and the average spherical shell thickness is 10-20nm; the preparation method is low in reaction temperature, short in time, easy to control and cheap in the used raw materials, thereby being beneficial to industrial production; and the prepared carbon hollow sphere is even in particle size and uniform in carbon shell thickness, and has favorable dispersity in solvent.
Description
Technical field
The present invention relates to a kind of nano-sized carbon hollow ball and preparation method thereof, belong to field of nano material preparation.
Background technology
The nano-sized carbon hollow material receives much concern because it has unique structure, low tap density, high-specific surface area, good heat and electrical conductivity.The carbon solid material is widely used in drug release, catalyzer, dye sensitization solar battery and novel energy-accumulation material.
In recent years, the method for preparing the nano-sized carbon hollow ball both at home and abroad has self-assembly method, spray pyrolysis, chemical Vapor deposition process and template.Wherein, template is the most frequently used method.Usually the template that adopts has silicon-dioxide, sodium salt and alloy cpd etc.The people such as Maria-Magdalena Titirici utilize hydrothermal method to form one deck carbon shell presoma (compound of polysaccharide) on the surface of template particles, then (usually above 600 ℃) heat-treat at a certain temperature, obtain the nucleocapsid structure after carbonization.Adopt finally certain solvent (hydrofluoric acid or sodium hydroxide) to dissolve inner template, to obtain final carbon shell [Adv.Funct.Mater., 17 (2007) 1010-1018].The people such as Yifeng Yu are take ionic liquid as novel carbon source, and employing silicon-dioxide is template, by the later stage high temperature cabonization and remove template procedure, obtain the controlled nano-sized carbon hollow material of size [J.Mater.Chem.A, 1 (2013) 1045-1047].The subject matter that above method exists at present has: the diameter of synthesis step long flow path, template is large, carbonization temperature is high and manufacturing cost is high.In addition, the hydrofluoric acid that goes template to adopt is violent in toxicity, has severe corrosive.
Summary of the invention
The objective of the invention is to be to provide a kind of preparation cost low spheroid epigranular, shell thickness homogeneous, and and the good nano-sized carbon hollow ball of solvent compatibility.
There are the problems such as long flow path, carbonization temperature is high, manufacturing cost is high in the preparation method who the present invention is directed to nano-sized carbon hollow ball of the prior art, another purpose is to be to provide that a kind of flow process is simple, the reaction times is short, the method for preparing the nano-sized carbon hollow ball that cost is low, nano-sized carbon hollow ball spheroid epigranular, shell thickness homogeneous that the method makes, and good with solvent compatibility.
The invention provides a kind of nano-sized carbon hollow ball, this nano-sized carbon hollow ball mean inside diameter is 20～30nm, and average spherical shell is thick is 10～20nm.
The acetylene black that described nano-sized carbon hollow ball is 30～50nm by nitric acid vapor oxidation median size makes.Described nitric acid vapor oxidation is with on the unsettled salpeter solution liquid level in closed reactor of acetylene black, reacting by heating still to 100～180 ℃, and the nitric acid vapor of generation carries out oxidizing reaction 2～12h to acetylene black; Described salpeter solution accounts for 5～30% of closed reactor volume; Described salpeter solution mass percent concentration is 65～68%; Described acetylene black and salpeter solution be 1g/6～30mL with magnitude relation.
The present invention also provides a kind of preparation method of nano-sized carbon hollow ball, this preparation method is with on the unsettled salpeter solution liquid level in closed reactor of acetylene black, reacting by heating still temperature to 100～180 ℃, the nitric acid vapor that produces carries out oxidizing reaction 2～12h to acetylene black, after reaction is completed,, with reaction product washing, drying, obtain; Described salpeter solution accounts for 5～30% of closed reactor volume.
The nano-sized carbon hollow ball mean inside diameter that described preparation method obtains is 20～30nm, and average spherical shell is thick is 10～20nm.
Described acetylene black and salpeter solution be 1g/6～30mL with magnitude relation.
Described salpeter solution mass percent concentration is 65～68%.
Described acetylene black median size is 30～50nm.
Described reaction product, at 110～130 ℃ of vacuum-drying 12～24h, obtains the nano-sized carbon hollow ball after using the distilled water repetitive scrubbing.
Described acetylene black is conventional industrial raw material.
Described acetylene black is unsettled is to load acetylene black by fixing core filter plate to realize.
The preparation method of nano-sized carbon hollow ball of the present invention, comprise the steps:
The first step, adding mass percent concentration in reactor is 65～68% salpeter solution, salpeter solution accounts for 5～30% of reactor volume;
Second step, load acetylene black on the core filter plate, the loading capacity of acetylene black is 1g/6～30mL with respect to salpeter solution; And the core filter plate is fixed on salpeter solution liquid level in reactor;
The 3rd the step, reactor is airtight, after being heated to 100～180 ℃, then the isothermal reaction time be 2～12h;
In the 4th step, make reactor cooling, then takes out the product on the core filter plate, adopts distilled water repeatedly after rinsing, dries 12～24h in the vacuum drying oven of 110～130 ℃, namely obtains the nano-sized carbon hollow ball.
Beneficial effect of the present invention: it is raw material that the present invention adopts industrial acetylene black first, and take nitric acid as oxygenant, oxidation makes the nano-sized carbon hollow ball to acetylene black by the high pressure nitric acid vapor.The present invention has advantages of following outstanding: the raw material of employing is other acetylene black of technical grade, and raw material is easy to get, with low cost; Realized in confined conditions making the nano-sized carbon hollow ball at the mild conditions of low temperature, short period of time, be conducive to suitability for industrialized production; The nano-sized carbon hollow ball granularity that makes by the inventive method is even, and carbon thickness of the shell homogeneous, and the product surface has abundant carboxylic group, has good wetting ability is easy to be scattered in water and general organic solvent.
Description of drawings
The equipment schematic diagram of [Fig. 1] preparation nano-sized carbon hollow ball of the present invention: 000 reaction under high pressure kettle barrel; 001 is polytetrafluoroethylcontainer container; 002 salpeter solution; 003 is acetylene black; 004 is the core filter plate; 005 is the funnel with the core filter plate.
[Fig. 2] is the transmission electron microscope picture of the prepared nano-sized carbon hollow ball of embodiment 1.
[Fig. 3] is the infrared contrast collection of illustrative plates of the prepared nano-sized carbon hollow ball of embodiment 1 and former acetylene black raw material.
Embodiment
Following examples are intended to that the invention will be further described, but are not the restriction the scope of protection of the invention.
Embodiment 1
Adding the mass percent concentration of 90 milliliters in a volume is the polytetrafluoroethylcontainer container of 500 milliliters is 65% concentrated nitric acid.The acetylene black powder that takes 3 gram median sizes and be 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container that adds concentrated nitric acid, regulate sand core funnel length so that the filter plate lower surface of sand core funnel be positioned on the concentrated nitric acid liquid level.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron to be sealed.Make the above-mentioned reactor that assembles be warmed up to 100 ℃, and after being incubated 12 hours, cooling, take out the product on filter plate, use rinsed with deionized water 5 times, then dried 12 hours in 120 ℃ of vacuum drying ovens, obtain nano hollow carbon of the present invention.Gained nano hollow carbon mean inside diameter is 30nm, and average spherical shell is thick is 10nm.Accompanying drawing 2 and accompanying drawing 3 are respectively transmission electron microscope picture and the infared spectrum of gained nano hollow carbon.Can find out from accompanying drawing 3 infared spectrums, gained nano hollow carbon ball is at wave number 1730cm
-1There is obvious carbonyl charateristic avsorption band at place, at 3430cm
-1Left and right has wider carboxyl to absorb broad peak, illustrates that the prepared nano hollow carbon ball of the present invention surface has abundant carboxylic group.
Embodiment 2
Adding the mass percent concentration of 25 milliliters in a volume is the polytetrafluoroethylcontainer container of 500 milliliters is 66% concentrated nitric acid.The acetylene black powder that takes 1 gram median size and be 50nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container that adds concentrated nitric acid, regulate sand core funnel length so that the filter plate lower surface of sand core funnel be positioned on the concentrated nitric acid liquid level.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron to be sealed.Make the above-mentioned reactor that assembles be warmed up to 180 ℃, and after being incubated 2 hours, cooling, take out the product on filter plate, use rinsed with deionized water 8 times, then dried 15 hours in 120 ℃ of vacuum drying ovens, obtain nano hollow carbon of the present invention.Gained nano hollow carbon mean inside diameter is 30nm, and average spherical shell is thick is 20nm.
Embodiment 3
Adding the mass percent concentration of 40 milliliters in a volume is the polytetrafluoroethylcontainer container of 500 milliliters is 67% concentrated nitric acid.The acetylene black powder that takes 1.5 gram median sizes and be 30nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container that adds concentrated nitric acid, regulate sand core funnel length so that the filter plate lower surface of sand core funnel be positioned on the concentrated nitric acid liquid level.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron to be sealed.Make the above-mentioned reactor that assembles be warmed up to 150 ℃, and after being incubated 5 hours, cooling, take out the product on filter plate, use rinsed with deionized water 10 times, then dried 12 hours in 120 ℃ of vacuum drying ovens, obtain nano hollow carbon of the present invention.Gained nano hollow carbon mean inside diameter is 20nm, and average spherical shell is thick is 10nm.
Embodiment 4
Adding the mass percent concentration of 60 milliliters in a volume is the polytetrafluoroethylcontainer container of 500 milliliters is 68% concentrated nitric acid.The acetylene black powder that takes 2 gram median sizes and be 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container that adds concentrated nitric acid, regulate sand core funnel length so that the filter plate lower surface of sand core funnel be positioned on the concentrated nitric acid liquid level.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron to be sealed.Make the above-mentioned reactor that assembles be warmed up to 150 ℃, and after being incubated 5 hours, cooling, take out the product on filter plate, use rinsed with deionized water 10 times, then dried 12 hours in 120 ℃ of vacuum drying ovens, obtain nano hollow carbon of the present invention.Gained nano hollow carbon mean inside diameter is 22nm, and average spherical shell is thick is 18nm.
Embodiment 5
Adding the mass percent concentration of 70 milliliters in a volume is the polytetrafluoroethylcontainer container of 500 milliliters is 67% concentrated nitric acid.The acetylene black powder that takes 2.5 gram median sizes and be 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container that adds concentrated nitric acid, regulate sand core funnel length so that the filter plate lower surface of sand core funnel be positioned on the concentrated nitric acid liquid level.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron to be sealed.Make the above-mentioned reactor that assembles be warmed up to 160 ℃, and after being incubated 6 hours, cooling, take out the product on filter plate, use rinsed with deionized water 10 times, then dried 12 hours in 120 ℃ of vacuum drying ovens, obtain nano hollow carbon of the present invention.Gained nano hollow carbon mean inside diameter is 26nm, and average spherical shell is thick is 14nm.
Embodiment 6
In being the polytetrafluoroethylcontainer container of 500 milliliters, a volume adds mass percent concentration 67% concentrated nitric acid of 150 milliliters.The acetylene black powder that takes 25 gram median sizes and be 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container that adds concentrated nitric acid, regulate sand core funnel length so that the filter plate lower surface of sand core funnel be positioned on the concentrated nitric acid liquid level.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron to be sealed.Make the above-mentioned reactor that assembles be warmed up to 180 ℃, and after being incubated 6 hours, cooling, take out the product on filter plate, use rinsed with deionized water 10 times, then dried 12 hours in 120 ℃ of vacuum drying ovens, obtain nano hollow carbon of the present invention.Gained nano hollow carbon mean inside diameter is 30nm, and average spherical shell is thick is 10nm.
Embodiment 7
Adding the mass percent concentration of 150 milliliters in a volume is the polytetrafluoroethylcontainer container of 500 milliliters is 67% concentrated nitric acid.The acetylene black powder that takes 5 gram median sizes and be 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container that adds concentrated nitric acid, regulate sand core funnel length so that the filter plate lower surface of sand core funnel be positioned on the concentrated nitric acid liquid level.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron to be sealed.Make the above-mentioned reactor that assembles be warmed up to 180 ℃, and after being incubated 4 hours, cooling, take out the product on filter plate, use rinsed with deionized water 10 times, then dried 12 hours in 120 ℃ of vacuum drying ovens, obtain nano hollow carbon of the present invention.Gained nano hollow carbon mean inside diameter is 25nm, and average spherical shell is thick is 15nm.
Embodiment 8
Adding the mass percent concentration of 150 milliliters in a volume is the polytetrafluoroethylcontainer container of 500 milliliters is 67% concentrated nitric acid.The acetylene black powder that takes 15 gram median sizes and be 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container that adds concentrated nitric acid, regulate sand core funnel length so that the filter plate lower surface of sand core funnel be positioned on the concentrated nitric acid liquid level.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron to be sealed.Making the above-mentioned reactor that assembles put into temperature is the baking oven of 180 ℃, is incubated after 3 hours, cooling, takes out the product on filter plate, and with rinsed with deionized water 10 times, then oven dry 12 hours in 120 ℃ of vacuum drying ovens, obtain nano hollow carbon of the present invention.Take out the product on filter plate, washing, suction filtration, in 120 ℃ of drying in oven.Gained nano hollow carbon mean inside diameter is 20nm, and average spherical shell is thick is 20nm.
Claims (8)
1. a nano-sized carbon hollow ball, is characterized in that, mean inside diameter is 20～30nm, and average spherical shell is thick is 10～20nm.
2. nano-sized carbon hollow ball as claimed in claim 1, is characterized in that, the acetylene black that described nano-sized carbon hollow ball is 30～50nm by nitric acid vapor oxidation median size makes.
3. nano-sized carbon hollow ball as claimed in claim 2, it is characterized in that, described nitric acid vapor oxidation is with on the unsettled salpeter solution liquid level in closed reactor of acetylene black, reacting by heating still to 100～180 ℃, and the nitric acid vapor of generation carries out oxidizing reaction 2～12h to acetylene black; Described salpeter solution accounts for 5～30% of closed reactor volume.
4. the preparation method of a nano-sized carbon hollow ball, it is characterized in that, on the unsettled salpeter solution liquid level in closed reactor of acetylene black, reacting by heating still temperature to 100～180 ℃, the nitric acid vapor that produces carries out oxidizing reaction 2～12h to acetylene black, after reaction is completed,, with reaction product washing, drying, obtain; Described salpeter solution accounts for 5～30% of closed reactor volume.
5. preparation method as claimed in claim 4, is characterized in that, the nano-sized carbon hollow ball mean inside diameter that obtains is 20～30nm, and average spherical shell is thick is 10～20nm.
6. preparation method as claimed in claim 4, is characterized in that, described acetylene black and salpeter solution be 1g/6～30mL with magnitude relation.
7. preparation method as claimed in claim 6, is characterized in that, described salpeter solution mass percent concentration is 65～68%.
8. preparation method as described in claim 3～7 any one, is characterized in that, described acetylene black median size is 30～50nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502342A (en) * | 2016-01-07 | 2016-04-20 | 上海工程技术大学 | Method for preparing nanometer hollow carbon spheres with dopamine serving as carbon source |
| CN107887618A (en) * | 2017-09-27 | 2018-04-06 | 姚乃元 | A kind of carbon-based platinum silver palladium ternary alloy catalyst and preparation method thereof |
| CN108091888A (en) * | 2017-12-13 | 2018-05-29 | 湖南省银峰新能源有限公司 | A kind of method of modifying of carbon felt for vanadium redox battery electrode |
| CN113540456A (en) * | 2021-06-04 | 2021-10-22 | 华南师范大学 | Metal oxide composite material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587032A (en) * | 2004-09-14 | 2005-03-02 | 武汉大学 | Hollow charcoal and its synthetic method and use |
| CN101993057A (en) * | 2009-08-27 | 2011-03-30 | 中国科学院金属研究所 | Method for preparing carbon hollow sphere |
-
2013
- 2013-08-09 CN CN201310346740.6A patent/CN103395773B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587032A (en) * | 2004-09-14 | 2005-03-02 | 武汉大学 | Hollow charcoal and its synthetic method and use |
| CN101993057A (en) * | 2009-08-27 | 2011-03-30 | 中国科学院金属研究所 | Method for preparing carbon hollow sphere |
Non-Patent Citations (1)
| Title |
|---|
| KATSUMI KAMEGAWA ET AL.: "OXIDATIVE DEGRADATION OF CARBON BLACKS WITH NITRIC ACID (I)-CHANGES IN PORE AND CRYSTALLOGRAPHIC STRUCTURES", 《CARBON》, vol. 36, no. 4, 31 December 1998 (1998-12-31), pages 433 - 441, XP004127680, DOI: doi:10.1016/S0008-6223(97)00227-3 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502342A (en) * | 2016-01-07 | 2016-04-20 | 上海工程技术大学 | Method for preparing nanometer hollow carbon spheres with dopamine serving as carbon source |
| CN107887618A (en) * | 2017-09-27 | 2018-04-06 | 姚乃元 | A kind of carbon-based platinum silver palladium ternary alloy catalyst and preparation method thereof |
| CN107887618B (en) * | 2017-09-27 | 2020-07-24 | 姚乃元 | Carbon-based platinum-silver-palladium ternary alloy catalyst and preparation method thereof |
| CN108091888A (en) * | 2017-12-13 | 2018-05-29 | 湖南省银峰新能源有限公司 | A kind of method of modifying of carbon felt for vanadium redox battery electrode |
| CN113540456A (en) * | 2021-06-04 | 2021-10-22 | 华南师范大学 | Metal oxide composite material and preparation method and application thereof |
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