CN100341779C - Solid process of preparing great amount of hollow nanometer carbon cage - Google Patents
Solid process of preparing great amount of hollow nanometer carbon cage Download PDFInfo
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- CN100341779C CN100341779C CNB2006100240886A CN200610024088A CN100341779C CN 100341779 C CN100341779 C CN 100341779C CN B2006100240886 A CNB2006100240886 A CN B2006100240886A CN 200610024088 A CN200610024088 A CN 200610024088A CN 100341779 C CN100341779 C CN 100341779C
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Abstract
The present invention relates to a method for preparing hollow nanometer carbon cages in a large scale under a solid state, which is used for the technical field of nanometer material preparation. The method has the technical scheme that a non-crystalline carbon precursor body with iron catalyst particles uniformly distributed in a large scale is firstly prepared, and then the precursor body is processed in a heat way to obtain the hollow nanometer carbon cages by a solid-state reaction, a catalyst of the hollow carbon nanometer cages is eliminated by post treatment finally, and final products are obtained. The method makes the temperature of the hollow carbon nanometer cages be directly grown at the solid state to be far lower than a literature report previously by using iron as the catalyst, and technological conditions are simplified. The hollow nanometer carbon cages can be prepared in a large scale by continuously supplying the catalyst of the precursor body and carbon sources in the process of preparation, a great amount of samples in a graphite crucible can be processed in a heat way once under the allowed condition of furnace chamber space of a high temperature furnace under the protection of inert gas, and the scale and large batch production can be realized; the patterns of the hollow nanometer carbon cages can be controlled by adjusting technological parameters in the whole process, and the method is easy to operate.
Description
Technical field
The present invention relates to a kind of method of the method for preparing nano cages, particularly a kind of solid-state preparing great amount of hollow nanometer carbon cage.Be used for the nano material preparation technical field.
Background technology
In recent years, the actual application value of carbon nanomaterial with and concrete manifestation in application more and more come into one's own, wherein hollow nano cages is owing to have unique physicochemical property, thus as form carbon-coating protection metallics in surfaces of metal nanoparticles; The different metallic element of deposition is made nanoscale electronic components etc. in its cavity; have broad application prospects; simultaneously; different applied environments needs the hollow nano cages of different diameter, wall thickness; have as the contrast table area that requirement needs that the nanocages diameter is little, wall is thin; then require certain diameter and wall thickness with proof strength when making lubricant; this has just determined to guarantee the production while of serialization and mass-producing; also need sample topography is controlled, solid-state direct growth method down is the shortcut of controlled a large amount of preparations just.The preparation method of hollow nano cages has used for reference the method that very high temperature directly prepares hollow nano cages, mainly contains the very high temperature of utilizing electric arc or laser to produce, and the thermolysis carbon raw material can directly make hollow nano cages; Perhaps use High Temperature Furnaces Heating Apparatus more than 2000 ℃, handle carbon source and directly make sample.But above method conversion unit complexity, output is few, can't be applied to actually operating.Thereby most methods is at first to prepare to be enclosed with the kernel nano cages, carry out subsequent disposal then and obtain hollow nano cages, but can subsequent disposal be removed the impurity kernel of nano cages totally disputable.
Find through literature search prior art, be mentioned to a kind of direct method for preparing the pure carbon nanocages in " Formation of Shell-Shaped CarbonNanoparticles Above Critical Laser Power in Irradiated Acetylene " (critical laser radiation acetylene prepares the shelly carbon nano-particle) literary composition that Huaihe Song etc. delivers on " Advanced Materials " (advanced material) (2004) 1721-1725, this method places reactor with quantitative acetylene, through the very high temperature that laser produces, thermolysis acetylene obtains to contain the hollow nano cages of a small amount of solid carbon nanocages.Though the method that relates in this method can Continuous Heat be decomposed acetylene generation pure carbon nanocages, uses laser as heating source, the temperature of reaction height, the equipment requirements height, not mentioned morphology control to sample still has distance from practical application.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, propose a kind of method of solid-state preparing great amount of hollow nanometer carbon cage.The present invention is by the vapor-phase reactant catalytic decomposition, and the precursor of continuous growth nano cages by the solid state reaction that the thermal treatment to precursor causes, can directly obtain the nano cages of internal structure hollow, and its content can reach cumulative volume more than 80%.Owing to precursor is that gas phase catalysis decomposes and to get, iron catalyst and solid-state carbon source mix, and precursor thermal treatment is subjected to the temperatures involved time long, so the hollow nano cages crystallization degree is high.By precursor being prepared the parameter adjustment of neutralization heat treatment process, pattern, the especially diameter that can effectively control hollow nano cages can control to the hundreds of nanometer from tens nanometers.
The present invention is achieved by the following technical solutions, the inventive method is divided into three steps, at first a large amount of preparations have the equally distributed amorphous carbon precursor of iron catalyst particle, then precursor is heat-treated by solid state reaction and obtain hollow nano cages, at last hollow nano cages is carried out subsequent disposal and remove catalyzer, promptly get final product.Particular content is as follows:
Step 1, preparation have the amorphous carbon precursor of catalyzer:
Rare gas element and acetylene gas are mixed, and the rare gas element flow velocity is the 16-60 liters per hour
-1The acetylene gas flow velocity is a 10-60 milliliter minute
-1, making rare gas element and acetylene ratio is 100: 1-40: between 9; Mixed gas is fed iron carbonyl liquid take catalyzer formation reactant gases out of, liquid is placed on the mixture of ice and water that immerses in the test tube by the vacuum flask insulation, makes iron carbonyl liquid remain 0 ℃; The main reactor temperature is risen to 550-800 ℃, and reactant gases is imported the main reactor top react through the high-temperature zone.In main reactor bottoms collector, obtained the equally distributed amorphous carbon precursor of iron catalyst particle continuously.
Step 2, thermal treatment precursor prepare hollow nano cages:
(1) precursor that step 1 is obtained places plumbago crucible to be placed on High Temperature Furnaces Heating Apparatus, and the feeding protection of inert gas that deflates;
(2) with High Temperature Furnaces Heating Apparatus from room temperature with 10 ℃ minutes
-1Speed is warming up to 1150-1550 ℃ of reaction high temperature;
(3) after High Temperature Furnaces Heating Apparatus reaches reaction high temperature, immediately at 10 ℃ minutes
-1Under the speed, lower the temperature 200-350 ℃; Immediately under identical speed, be warming up to former reaction high temperature after cooling finishes, this process is carried out twice.
(4) after High Temperature Furnaces Heating Apparatus reaches reaction high temperature once more, immediately at 10 ℃ minutes
-1Under the speed, be cooled to 800-650 ℃; Close the High Temperature Furnaces Heating Apparatus power supply subsequently, make sample cool to room temperature with the furnace, promptly get hollow nano cages.
Removing of step 3, remainder catalyst:
(1) hollow nano cages that step 2 is obtained places concentrated hydrochloric acid (37vol.%) or pure salpeter solution, places ultrasonator to carry out sonic oscillation this miscellany then, and the time is 1～3 hour;
(2) mixture after will vibrating is 100-200 ℃ of heating down, and adds the recirculated water reflux cooling, and the time is 3～6 hours:
(3) with gained mixture adding distil water dilution in the above-mentioned steps, use filtering with microporous membrane, behind distilled water wash, oven dry promptly gets the hollow nano cages of removing remainder catalyst immediately.
The present invention by the solid state reaction that the thermal treatment to precursor causes, can directly obtain the high crystallization degree nano cages of internal structure hollow under the protection of rare gas element.The preparation of precursor is to utilize the catalytic effect of transition metal nanoparticles that acetylene is decomposed, and through chemical vapour deposition, the equally distributed amorphous carbon powder of iron catalyst particle is arranged in vertical floating catalytic Reaktionsofen, promptly is precursor.After the thermal treatment, hollow nano cages is carried out pickling remove remainder catalyst.By adjusting rare gas element and acetylene gas ratio in the precursor preparation; Or adjust heat treated temperature, the hollow nano cages diameter can control to 200 nanometers from tens nanometers, when the nanocages diameter Distribution in the 10-20 nanometer, detect to such an extent that its wall thickness is 2～5nm, the graphite number of plies is 6～15 layers; Diameter Distribution is in the 60-200 nanometer, and its wall thickness is 7～25nm, and the graphite number of plies is 20～75 layers.The device that this method is used is simple, is easy to control, is suitable for serialization, industrial and large-scale production.
Iron of the present invention is as the use of catalyzer, and the temperature that makes solid-state direct growth hollow nano cages has down been simplified processing condition far below previous bibliographical information.In the preparation process, the catalyzer and the carbon source of precursor provide continuously, but mass production; Under the protection of rare gas element, under the condition that allows in High Temperature Furnaces Heating Apparatus burner hearth space, but the sample in the numerous plumbago crucibles of thermal treatment is once realized mass-producing, large batch of production; Whole process is by adjusting process parameter, the pattern of may command hollow nano cages, easy handling.
Embodiment
The device that the inventive method adopts comprises gas inlet, gas flow valve, heating resistor stove, main reactor, product collection device, waste gas filter, plumbago crucible, vacuum pump, resistance High Temperature Furnaces Heating Apparatus.During enforcement, take certain flow rate rare gas element and acetylene mixing feeding iron carbonyl liquid out of catalyzer formation reactant gases introducing main reactor.In main reactor, reaction raw materials has the equally distributed amorphous carbon precursor of iron catalyst particle through decomposition, formation of deposits, and in the product collection bottom of device, waste gas is then discharged through waste gas filter in the effect deposit of carrying gas; Precursor places plumbago crucible to be placed on High Temperature Furnaces Heating Apparatus, and the feeding protection of inert gas that deflates, and heat-treats, reduce to after the room temperature hollow nano cages.
Content and above device below in conjunction with the inventive method provide specific embodiment:
Embodiment one:
Step 1, preparation have the amorphous carbon precursor of catalyzer:
Nitrogen and acetylene gas are mixed, and the nitrogen gas flow velocity is 60 liters per hours
-1The acetylene gas flow velocity is 10 milliliters minutes
-1, making rare gas element and acetylene ratio is 100: 1; Mixed gas is fed iron carbonyl liquid take catalyzer formation reactant gases out of, liquid is placed on the mixture of ice and water that immerses in the test tube by the vacuum flask insulation, makes iron carbonyl liquid remain 0 ℃; The main reactor temperature is risen to 800 ℃, and reactant gases is imported the main reactor top react through the high-temperature zone.In main reactor bottoms collector, obtained the equally distributed amorphous carbon precursor of iron catalyst particle continuously.
Step 2, thermal treatment precursor prepare hollow nano cages:
(1) precursor that step 1 is obtained places plumbago crucible to be placed on High Temperature Furnaces Heating Apparatus, and the feeding protection of inert gas that deflates;
(2) with High Temperature Furnaces Heating Apparatus from room temperature with 10 ℃ minutes
-1Speed is warming up to 1550 ℃ of reaction high temperature;
(3) after High Temperature Furnaces Heating Apparatus reaches reaction high temperature, immediately at 10 ℃ minutes
-1Under the speed, lower the temperature 200 ℃; Immediately under identical speed, be warming up to former reaction high temperature after cooling finishes, this process is carried out twice.
(4) after High Temperature Furnaces Heating Apparatus reaches reaction high temperature once more, immediately at 10 ℃ minutes
-1Under the speed, be cooled to 750 ℃; Close the High Temperature Furnaces Heating Apparatus power supply subsequently, make sample cool to room temperature with the furnace, promptly get hollow nano cages.
Removing of step 3, remainder catalyst:
(1) hollow nano cages that step 2 is obtained places concentrated hydrochloric acid (37vol.%) solution, places ultrasonator to carry out sonic oscillation this miscellany then, and the time is 3 hours;
(2) mixture after will vibrating is 150 ℃ of heating down, and adds the recirculated water reflux cooling, and the time is 4 hours;
(3) with gained mixture adding distil water dilution in the above-mentioned steps, use filtering with microporous membrane, behind distilled water wash, oven dry promptly gets the hollow nano cages of removing remainder catalyst immediately.
Implementation result: at first make the precursor that contains iron particle, get hollow nano cages after the thermal treatment, remainder catalyst is fallen in last pickling, and the mean diameter 60～200nm of nano cages, its wall thickness are 7～25nm, and the graphite number of plies is 20～75 layers.
Embodiment two:
Step 1, preparation have the amorphous carbon precursor of catalyzer:
Nitrogen and acetylene gas are mixed, and the nitrogen gas flow velocity is 10 liters per hours
-1The acetylene gas flow velocity is 60 milliliters minutes
-1, making rare gas element and acetylene ratio is 40: 9; Mixed gas is fed iron carbonyl liquid take catalyzer formation reactant gases out of, liquid is placed on the mixture of ice and water that immerses in the test tube by the vacuum flask insulation, makes iron carbonyl liquid remain 0 ℃; The main reactor temperature is risen to 550 ℃, and reactant gases is imported the main reactor top react through the high-temperature zone.In main reactor bottoms collector, obtained the equally distributed amorphous carbon precursor of iron catalyst particle continuously.
Step 2, thermal treatment precursor prepare hollow nano cages:
(1) precursor that step 1 is obtained places plumbago crucible to be placed on High Temperature Furnaces Heating Apparatus, and the feeding protection of inert gas that deflates;
(2) with High Temperature Furnaces Heating Apparatus from room temperature with 10 ℃ minutes
-1Speed is warming up to 1450 ℃ of reaction high temperature;
(3) after High Temperature Furnaces Heating Apparatus reaches reaction high temperature, immediately at 10 ℃ minutes
-1Under the speed, lower the temperature 250 ℃; Immediately under identical speed, be warming up to former reaction high temperature after cooling finishes, this process is carried out twice.
(4) when High Temperature Furnaces Heating Apparatus reach react high temperature once more after, immediately at 10 ℃ minutes
-1Under the speed, be cooled to 800 ℃; Close the High Temperature Furnaces Heating Apparatus power supply subsequently, make sample cool to room temperature with the furnace, promptly get hollow nano cages.
Removing of step 3, remainder catalyst:
(1) hollow nano cages that step 2 is obtained places pure salpeter solution, places ultrasonator to carry out sonic oscillation this miscellany then, and the time is 1 hour;
(2) mixture after will vibrating is 200 ℃ of heating down, and adds the recirculated water reflux cooling, and the time is 3 hours;
(3) with gained mixture adding distil water dilution in the above-mentioned steps, use filtering with microporous membrane, behind distilled water wash, oven dry promptly gets the hollow nano cages of removing remainder catalyst immediately.
Implementation result: at first make the precursor that contains iron particle, get hollow nano cages after the thermal treatment, remainder catalyst is fallen in last pickling, and the mean diameter 20～35nm of nano cages, its wall thickness are 5～10nm, and the graphite number of plies is 15～30 layers.
Embodiment three:
Step 1, preparation have the amorphous carbon precursor of catalyzer:
Nitrogen and acetylene gas are mixed, and the nitrogen gas flow velocity is 30 liters per hours
-1The acetylene gas flow velocity is 20 milliliters minutes
-1, making rare gas element and acetylene ratio is 25: 1; Mixed gas is fed iron carbonyl liquid take catalyzer formation reactant gases out of, liquid is placed on the mixture of ice and water that immerses in the test tube by the vacuum flask insulation, makes iron carbonyl liquid remain 0 ℃; The main reactor temperature is risen to 700 ℃, and reactant gases is imported the main reactor top react through the high-temperature zone.In main reactor bottoms collector, obtained the equally distributed amorphous carbon precursor of iron catalyst particle continuously.
Step 2, thermal treatment precursor prepare hollow nano cages:
(1) precursor that step 1 is obtained places plumbago crucible to be placed on High Temperature Furnaces Heating Apparatus, and the feeding protection of inert gas that deflates;
(2) with High Temperature Furnaces Heating Apparatus from room temperature with 10 ℃ minutes
-1Speed is warming up to 1150 ℃ of reaction high temperature;
(3) after High Temperature Furnaces Heating Apparatus reaches reaction high temperature, immediately at 10 ℃ minutes
-1Under the speed, lower the temperature 350 ℃; Immediately under identical speed, be warming up to former reaction high temperature after cooling finishes, this process is carried out twice.
(4) when High Temperature Furnaces Heating Apparatus reach react high temperature once more after, immediately at 10 ℃ minutes
-1Under the speed, be cooled to 650 ℃; Close the High Temperature Furnaces Heating Apparatus power supply subsequently, make sample cool to room temperature with the furnace, promptly get hollow nano cages.
Removing of step 3, remainder catalyst:
(1) hollow nano cages that step 2 is obtained places concentrated hydrochloric acid (37vol.%) solution, places ultrasonator to carry out sonic oscillation this miscellany then, and the time is 2 hours;
(2) mixture after will vibrating is 100 ℃ of heating down, and adds the recirculated water reflux cooling, and the time is 6 hours;
(3) with gained mixture adding distil water dilution in the above-mentioned steps, use filtering with microporous membrane, behind distilled water wash, oven dry promptly gets the hollow nano cages of removing remainder catalyst immediately.
Implementation result: at first make the precursor that contains iron particle, get hollow nano cages after the thermal treatment, remainder catalyst is fallen in last pickling, and the mean diameter 10～25nm of nano cages, its wall thickness are 2～7nm, and the graphite number of plies is 6～20 layers.
Claims (6)
1, a kind of method of solid-state preparing great amount of hollow nanometer carbon cage is characterized in that:
Step 1, preparation have the amorphous carbon precursor of catalyzer:
Rare gas element and acetylene gas mixture are fed 0 ℃ iron carbonyl liquid to be taken catalyzer out of and forms reactant gases, reactant gases is imported the main reactor top react, in main reactor bottoms collector, obtained the equally distributed amorphous carbon precursor of iron catalyst particle continuously through 550～800 ℃ of high-temperature zones;
Step 2, thermal treatment precursor prepare hollow nano cages:
(1) precursor that step 1 is obtained places High Temperature Furnaces Heating Apparatus, and the feeding protection of inert gas that deflates;
(2) High Temperature Furnaces Heating Apparatus slowly is warming up to 1150-1550 ℃ from room temperature, heat-up rate is 10 ℃ minutes
-1
(3) after High Temperature Furnaces Heating Apparatus reaches 1150-1550 ℃, slowly to lower the temperature immediately 200-350 ℃, cooling slowly is warming up to 1150-1550 ℃ after finishing immediately, and this process carries out twice, and cooling and the speed that heats up are 10 ℃ minutes
-1
(4) after High Temperature Furnaces Heating Apparatus reaches 1150-1550 ℃ of reaction high temperature once more, slowly be cooled to 800-650 ℃ immediately, cooling rate is 10 ℃ minutes
-1, close the High Temperature Furnaces Heating Apparatus power supply subsequently, make sample cool to room temperature with the furnace, promptly get hollow nano cages;
Removing of step 3, remainder catalyst:
(1) hollow nano cages that step 2 is obtained places concentrated hydrochloric acid or pure salpeter solution, places ultrasonator to carry out sonic oscillation this miscellany then;
(2) mixture heating up after will vibrating, and add the recirculated water reflux cooling;
(3) with gained mixture adding distil water dilution in the above-mentioned steps, use filtering with microporous membrane, behind distilled water wash, oven dry promptly gets the hollow nano cages of removing remainder catalyst immediately.
2, the method for solid-state preparing great amount of hollow nanometer carbon cage according to claim 1 is characterized in that, in the step 1, with rare gas element and acetylene ratio control 100: 1-40: feed iron carbonyl liquid between 9 and take catalyzer out of and form reactant gases.
According to the method for claim 1 or 2 described solid-state preparing great amount of hollow nanometer carbon cage, it is characterized in that 3, in the step 1, described rare gas element flow velocity is the 16-60 liters per hour
-1
According to the method for claim 1 or 2 described solid-state preparing great amount of hollow nanometer carbon cage, it is characterized in that 4, in the step 1, described acetylene gas flow velocity is a 10-60 milliliter minute
-1
5, the method for solid-state preparing great amount of hollow nanometer carbon cage according to claim 1 is characterized in that, in the step 3, described (1), and the concentration of concentrated hydrochloric acid is 37vol.%, the sonic oscillation time is 1～3 hour.
6, the method for solid-state preparing great amount of hollow nanometer carbon cage according to claim 1 is characterized in that, in the step 3, described (2) are heated the mixture after the vibration down at 100-200 ℃, and added the recirculated water reflux cooling, and the time is 3～6 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003050036A1 (en) * | 2001-12-11 | 2003-06-19 | Nanomix Inc. | Increasing hydrogen adsorption of nanostructures storage materials by modifying sp2 covalent bonds |
| CN1583552A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Method for mass preparing hollow nanometer carbon cages |
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| WO2003050036A1 (en) * | 2001-12-11 | 2003-06-19 | Nanomix Inc. | Increasing hydrogen adsorption of nanostructures storage materials by modifying sp2 covalent bonds |
| CN1583552A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Method for mass preparing hollow nanometer carbon cages |
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