CN103395773B - Nano carbon hollow sphere and preparation method thereof - Google Patents
Nano carbon hollow sphere and preparation method thereof Download PDFInfo
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- CN103395773B CN103395773B CN201310346740.6A CN201310346740A CN103395773B CN 103395773 B CN103395773 B CN 103395773B CN 201310346740 A CN201310346740 A CN 201310346740A CN 103395773 B CN103395773 B CN 103395773B
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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 carbon hollow sphere and preparation method thereof, belong to field of nano material preparation.
Background technology
Nano-sized carbon hollow material receives much concern because it has unique structure, low tap density, high-specific surface area, excellent heat and electrical conductivity.Carbon solid material is widely used in drug release, catalyzer, dye sensitization solar battery and novel energy-accumulation material.
In recent years, the method preparing Nano carbon hollow sphere 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.The template of usual employing 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 DEG C) heat-treat at a certain temperature, obtain the nucleocapsid structure after carbonization.Certain solvent (hydrofluoric acid or sodium hydroxide) is finally adopted to dissolve inner template, to obtain final carbon shell [Adv.Funct.Mater., 17 (2007) 1010-1018].The people such as Yifeng Yu are novel carbon source with ionic liquid, and employing silicon-dioxide is template, by 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 comparatively large, carbonization temperature is high and manufacturing cost is high.In addition, the hydrofluoric acid going template to adopt is violent in toxicity, has severe corrosive.
Summary of the invention
The object of the invention is to be to provide a kind of preparation cost low, spheroid epigranular, shell thickness are homogeneous, and the Nano carbon hollow sphere good with solvent compatibility.
There is the problems such as long flow path, carbonization temperature is high, manufacturing cost is high in the preparation method that the present invention is directed to Nano carbon hollow sphere of the prior art, another object is to provide that a kind of flow process is simple, the reaction times is short, the method of Nano carbon hollow sphere that what cost was low prepare, the Nano carbon hollow sphere spheroid epigranular that the method obtains, shell thickness are homogeneous, and good with solvent compatibility.
The invention provides a kind of Nano carbon hollow sphere, this Nano carbon hollow sphere mean inside diameter is 20 ~ 30nm, and average spherical shell is thick is 10 ~ 20nm.
The acetylene black that described Nano carbon hollow sphere is 30 ~ 50nm by nitric acid vapor oxidation median size obtains.Described nitric acid vapor oxidation is that reacting by heating still is to 100 ~ 180 DEG C, and the nitric acid vapor of generation carries out oxidizing reaction 2 ~ 12h to acetylene black by unsettled for the acetylene black salpeter solution liquid level in closed reactor; 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.
Present invention also offers a kind of preparation method of Nano carbon hollow sphere, this preparation method is by unsettled for the acetylene black salpeter solution liquid level in closed reactor, reacting by heating still temperature is to 100 ~ 180 DEG C, the nitric acid vapor produced carries out oxidizing reaction 2 ~ 12h to acetylene black, after having reacted, by reaction product washing, drying, to obtain final product; Described salpeter solution accounts for 5 ~ 30% of closed reactor volume.
The Nano carbon hollow sphere 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.
After described reaction product distilled water repetitive scrubbing, at 110 ~ 130 DEG C of vacuum-drying 12 ~ 24h, obtain Nano carbon hollow sphere.
Described acetylene black is conventional industrial raw material.
Described acetylene black is unsettled is load acetylene black by fixing core filter plate to realize.
The preparation method of Nano carbon hollow sphere of the present invention, comprises the steps:
The first step, add the salpeter solution that mass percent concentration is 65 ~ 68% in a kettle., salpeter solution accounts for 5 ~ 30% of reactor volume;
Second step, core filter plate loads acetylene black, and the loading capacity of acetylene black is 1g/6 ~ 30mL relative to salpeter solution; And core filter plate is fixed on salpeter solution liquid level in a kettle.;
3rd step, reactor is airtight, after being heated to 100 ~ 180 DEG C, then the isothermal reaction time be 2 ~ 12h;
4th step, makes reactor cool, and then takes out the product on core filter plate, adopts distilled water repeatedly after rinsing, dries 12 ~ 24h, namely obtain Nano carbon hollow sphere in the vacuum drying oven of 110 ~ 130 DEG C.
Beneficial effect of the present invention: the present invention adopts industrial acetylene black to be raw material first take nitric acid as oxygenant, by high pressure nitric acid steam to the obtained Nano carbon hollow sphere of acetylene black oxidation.The present invention has following outstanding advantage: the raw material of employing is other acetylene black of technical grade, and raw material is easy to get, with low cost; Achieve in confined conditions and obtain Nano carbon hollow sphere at the mild conditions of low temperature, short period of time, be conducive to suitability for industrialized production; By the Nano carbon hollow sphere epigranular that the inventive method is obtained, carbon thickness of the shell is homogeneous, and its surface has abundant carboxylic group, has good wetting ability, is easy to be scattered in water and general organic solvent.
Accompanying drawing explanation
[Fig. 1] prepares the equipment schematic diagram of Nano carbon hollow sphere of the present invention: 000 reaction under high pressure kettle barrel; 001 is polytetrafluoroethylcontainer container; 002 salpeter solution; 003 is acetylene black; 004 is core filter plate; 005 for being with the funnel of core filter plate.
The transmission electron microscope picture of [Fig. 2] Nano carbon hollow sphere prepared by embodiment 1.
[Fig. 3] Nano carbon hollow sphere prepared by embodiment 1 and the infrared contrast collection of illustrative plates of former acetylene black raw material.
Embodiment
Following examples are intended to that the invention will be further described, but are not restriction the scope of protection of the invention.
Embodiment 1
Be the mass percent concentration adding 90 milliliters in the polytetrafluoroethylcontainer container of 500 milliliters at a volume be 65% concentrated nitric acid.Taking 3 grams of median sizes is that the acetylene black powder of 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container having added concentrated nitric acid, regulate the length of sand core funnel to be positioned on concentrated nitric acid liquid level to make the filter plate lower surface of sand core funnel.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron seal.Make the above-mentioned reactor assembled be warmed up to 100 DEG C, and after being incubated 12 hours, cooling, take out the product on filter plate, by rinsed with deionized water 5 times, then dry 12 hours in 120 DEG C 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.As can be seen from accompanying drawing 3 infared spectrum, 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 nano hollow carbon ball surface obtained by the present invention has abundant carboxylic group.
Embodiment 2
Be the mass percent concentration adding 25 milliliters in the polytetrafluoroethylcontainer container of 500 milliliters at a volume be 66% concentrated nitric acid.Taking 1 gram of median size is that the acetylene black powder of 50nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container having added concentrated nitric acid, regulate the length of sand core funnel to be positioned on concentrated nitric acid liquid level to make the filter plate lower surface of sand core funnel.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron seal.Make the above-mentioned reactor assembled be warmed up to 180 DEG C, and after being incubated 2 hours, cooling, take out the product on filter plate, by rinsed with deionized water 8 times, then dry 15 hours in 120 DEG C 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
Be the mass percent concentration adding 40 milliliters in the polytetrafluoroethylcontainer container of 500 milliliters at a volume be 67% concentrated nitric acid.Taking 1.5 grams of median sizes is that the acetylene black powder of 30nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container having added concentrated nitric acid, regulate the length of sand core funnel to be positioned on concentrated nitric acid liquid level to make the filter plate lower surface of sand core funnel.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron seal.Make the above-mentioned reactor assembled be warmed up to 150 DEG C, and after being incubated 5 hours, cooling, take out the product on filter plate, by rinsed with deionized water 10 times, then dry 12 hours in 120 DEG C 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
Be the mass percent concentration adding 60 milliliters in the polytetrafluoroethylcontainer container of 500 milliliters at a volume be 68% concentrated nitric acid.Taking 2 grams of median sizes is that the acetylene black powder of 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container having added concentrated nitric acid, regulate the length of sand core funnel to be positioned on concentrated nitric acid liquid level to make the filter plate lower surface of sand core funnel.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron seal.Make the above-mentioned reactor assembled be warmed up to 150 DEG C, and after being incubated 5 hours, cooling, take out the product on filter plate, by rinsed with deionized water 10 times, then dry 12 hours in 120 DEG C 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
Be the mass percent concentration adding 70 milliliters in the polytetrafluoroethylcontainer container of 500 milliliters at a volume be 67% concentrated nitric acid.Taking 2.5 grams of median sizes is that the acetylene black powder of 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container having added concentrated nitric acid, regulate the length of sand core funnel to be positioned on concentrated nitric acid liquid level to make the filter plate lower surface of sand core funnel.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron seal.Make the above-mentioned reactor assembled be warmed up to 160 DEG C, and after being incubated 6 hours, cooling, take out the product on filter plate, by rinsed with deionized water 10 times, then dry 12 hours in 120 DEG C 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
Be in the polytetrafluoroethylcontainer container of 500 milliliters, add mass percent concentration 67% concentrated nitric acid of 150 milliliters at a volume.Taking 25 grams of median sizes is that the acetylene black powder of 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container having added concentrated nitric acid, regulate the length of sand core funnel to be positioned on concentrated nitric acid liquid level to make the filter plate lower surface of sand core funnel.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron seal.Make the above-mentioned reactor assembled be warmed up to 180 DEG C, and after being incubated 6 hours, cooling, take out the product on filter plate, by rinsed with deionized water 10 times, then dry 12 hours in 120 DEG C 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
Be the mass percent concentration adding 150 milliliters in the polytetrafluoroethylcontainer container of 500 milliliters at a volume be 67% concentrated nitric acid.Taking 5 grams of median sizes is that the acetylene black powder of 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container having added concentrated nitric acid, regulate the length of sand core funnel to be positioned on concentrated nitric acid liquid level to make the filter plate lower surface of sand core funnel.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron seal.Make the above-mentioned reactor assembled be warmed up to 180 DEG C, and after being incubated 4 hours, cooling, take out the product on filter plate, by rinsed with deionized water 10 times, then dry 12 hours in 120 DEG C 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
Be the mass percent concentration adding 150 milliliters in the polytetrafluoroethylcontainer container of 500 milliliters at a volume be 67% concentrated nitric acid.Taking 15 grams of median sizes is that the acetylene black powder of 40nm is placed on the filter plate of sand core funnel.Sand core funnel is put into the polytetrafluoroethylcontainer container having added concentrated nitric acid, regulate the length of sand core funnel to be positioned on concentrated nitric acid liquid level to make the filter plate lower surface of sand core funnel.Above-mentioned polytetrafluoroethylcontainer container is put into stainless steel cauldron seal.Make the above-mentioned reactor assembled put into the baking oven that temperature is 180 DEG C, be incubated after 3 hours, cooling, take out the product on filter plate, by rinsed with deionized water 10 times, then dry 12 hours in 120 DEG C of vacuum drying ovens, obtain nano hollow carbon of the present invention.Take out the product on filter plate, washing, suction filtration, in 120 DEG C of drying in oven.Gained nano hollow carbon mean inside diameter is 20nm, and average spherical shell is thick is 20nm.
Claims (4)
1. the preparation method of a Nano carbon hollow sphere, it is characterized in that, by on unsettled for the acetylene black salpeter solution liquid level in closed reactor, reacting by heating still temperature is to 100 ~ 180 DEG C, the nitric acid vapor produced carries out oxidizing reaction 2 ~ 12h to acetylene black, after having reacted, by reaction product washing, drying, obtaining mean inside diameter is 20 ~ 30nm, and average spherical shell is thick is the Nano carbon hollow sphere of 10 ~ 20nm; Described salpeter solution accounts for 5 ~ 30% of closed reactor volume.
2. preparation method as claimed in claim 1, is characterized in that, described acetylene black and salpeter solution be 1g/6 ~ 30mL with magnitude relation.
3. preparation method as claimed in claim 2, it is characterized in that, described salpeter solution mass percent concentration is 65 ~ 68%.
4. the preparation method as described in any one of claims 1 to 3, is characterized in that, described acetylene black median size is 30 ~ 50nm.
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| 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 |
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