CN100372761C - Method for preparing hollow Nano carbon balls in graphite structure under solid state - Google Patents
Method for preparing hollow Nano carbon balls in graphite structure under solid state Download PDFInfo
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- CN100372761C CN100372761C CNB2006100279922A CN200610027992A CN100372761C CN 100372761 C CN100372761 C CN 100372761C CN B2006100279922 A CNB2006100279922 A CN B2006100279922A CN 200610027992 A CN200610027992 A CN 200610027992A CN 100372761 C CN100372761 C CN 100372761C
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Abstract
The present invention relates to a method for preparing hollow nanometer carbon balls with a graphite structure under a solid state, which belongs to the technical field of nanometer material preparation. The method comprises the three steps: a non-crystalline carbon precursor body with iron catalyst particles uniformly distributed is prepared in a large scale firstly, and then the precursor body is processed in a heat way by solid-state reaction under different temperature rise speeds to obtain a hollow graphite nanometer structure, a catalyst of hollow graphite nanometer particles is eliminated by post treatment finally, and final products are obtained. The method simplifies technological conditions by adopting iron as the catalyst, the hollow nanometer carbon balls can be prepared in a large scale by continuously supplying the catalyst of the precursor body and carbon sources in the process of preparation, and patterns of the products can be controlled when the hollow graphite nanometer particles are directly obtained by using different temperature rise speeds and different iron catalyst and carbon source reaction situations under the protection of inert gas. The method has the advantages of simple devices and easy operation.
Description
Technical field
The present invention relates to a kind of method of nano material preparation technical field, particularly a kind of in the solid-state method for preparing the graphite-structure hollow Nano carbon balls down.
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 the hollow plumbago nanostructure is made nanoscale electronic components owing to have unique physicochemical property as the different metallic element of deposition in its cavity; Easily introduce multiple functional group at hollow plumbago nanostructure outside surface and be used for biomedicine field etc., have broad application prospects, this has just determined to need to simplify hollow plumbago nanostructure preparation condition, realizes scale preparation, to satisfy the requirement of using.
The preparation method of graphite-structure hollow Nano carbon balls has used for reference the method that high temperature directly prepares hollow nano cages, mainly contains the high temperature that utilizes electric arc or laser to produce, and the thermolysis carbon raw material can directly make the hollow plumbago nanostructure; Perhaps use sol-gel method, react for a long time through multistep, preparation metal-salt and the mixed uniformly aerogel precursor body of carbon source directly prepare the hollow plumbago nanostructure by the thermal treatment more than 1000 ℃ again.Above method is not the conversion unit complexity, and output is few, is exactly that reactions steps is many, and the time is long and control morphology change is still not mentioned.Difficulty is applied to actually operating.The present invention utilizes under the different heat-up rates, and iron catalyst is different with the carbon source response situation, controls the pattern of product when greatly having reduced temperature of reaction effectively, has reduced direct preparation hollow plumbago nanostructure condition, has improved output.
Find through literature search prior art, mention the use sol-gel method in " Catalytic graphitization ofcarbon aerogels by transition metals " (utilizing transition metal-catalyzed graphitized carbon aerogel) literary composition that F.J.Maldonado-Ho ' dar etc. deliver on " Langmuir " (Langmuir) 14 (2000) 4367-4373, react for a long time through multistep, preparation metal-salt and the mixed uniformly aerogel precursor body of carbon source, the thermal treatment by 1000-1800 ℃ directly prepares the hollow plumbago nanostructure again.Though can obtain the hollow plumbago nanostructure, reactions steps is a lot, the time is long to surpass a week, and sample particle is bigger, all more than tens nanometers, wall thickness is thicker, more than 4 nanometers, have with a certain 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 in the solid-state method for preparing the graphite-structure hollow Nano carbon balls down.The present invention adopts 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 graphite structure of internal structure hollow, and its content can reach cumulative volume more than 80%.Owing to precursor is that the gas phase catalysis decomposition gets, only a few nanometer iron catalysts and solid-state carbon source mix, and under the catalysis of iron nano-particle, temperature of reaction reduces greatly; Under different heat-up rates, iron catalyst is different with the carbon source response situation, controls the pattern of product simultaneously effectively (heat-up rate is fast, and the iron particle is not grown up in temperature-rise period, catalysis and the carbon nano-particle that comes is little greatly having reduced temperature of reaction; Slow as heat-up rate, otherwise then).
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 to precursor under different heat-up rates, heat-treat and pass through solid state reaction, obtain the hollow plumbago nanostructure, at last the hollow plumbago nano particle 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 10-60 liters per hour
-1The acetylene gas flow velocity is a 10-60 milliliter minute
-1, making rare gas element and acetylene ratio is 100: 1-25: between 9; Mixed gas is fed iron carbonyl liquid take catalyzer formation reactant gases out of, liquid is placed on and immerses mixture of ice and water in the test tube, makes iron carbonyl liquid remain 0 ℃; The main reactor temperature is risen to 550-850 ℃, 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 the hollow plumbago nanostructure:
Sample is placed vitrified pipe, and vacuumizing also feeds protection of inert gas.High Temperature Furnaces Heating Apparatus is warming up to 700-1150 ℃ of reaction high temperature from room temperature, after reaching temperature of reaction, with the high-temperature zone that vitrified pipe inserts stove, control heat-up rate 200-2000 ℃ minute
-1, and be incubated 5-120 minute, and close the High Temperature Furnaces Heating Apparatus power supply subsequently, make sample cool to room temperature with the furnace, extract long test tube after perhaps soaking time arrives immediately out, place the room temperature environment air cooling to room temperature, repeat above process 0-4 time, to improve transformation efficiency.Promptly get the hollow plumbago nanostructure.
Removing of step 3, remainder catalyst:
(1) the hollow plumbago nanostructure that step 2 is obtained places pure nitric acid and concentrated hydrochloric acid (37vol.%) mixing solutions, and mixed volume places this miscellany ultrasonator to carry out sonic oscillation than for 0-25% then, and the time is 0.5～3 hour;
(2) mixture after will vibrating is 60-120 ℃ of heating down, and adds the recirculated water reflux cooling, and the time is 1～6 hour;
(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 graphite-structure hollow Nano carbon balls of removing remainder catalyst immediately.
The present invention is under the protection of rare gas element; the solid state reaction that causes by thermal treatment to precursor; utilize under the different heat-up rates, iron catalyst is different with the carbon source response situation, the pattern of control product in the graphite-structure Nano carbon balls that directly obtains hollow.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, the hollow plumbago nanostructure is carried out pickling remove remainder catalyst.The present invention is by sending precursor into the high-temperature zone, and the control heat-up rate under the katalysis of iron, reduces graphitization temperature greatly, far below the fusing point of carbon, grows the hollow plumbago nanostructure under solid-state.Hollow plumbago nano particle mean diameter is in the 3-60 nanometer, and the graphite number of plies is 1～25 layer and does not wait; The device that this method is used is simple, is suitable for serialization, industrial and large-scale production.
The present invention adopts iron as 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, utilize under the different heat-up rates, iron catalyst is different with the carbon source response situation, the pattern of control product in the graphite nanoparticles that directly obtains hollow, equipment is simple, easy handling.
Embodiment
The device that the inventive method adopts comprises the corundum or the quartzy long test tube of gas inlet, gas flow valve, heating resistor stove, main reactor, product collection device, waste gas filter, vacuum pump, resistance High Temperature Furnaces Heating Apparatus, end sealing.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 product is deposited on the collection device bottom under the effect of carrying gas, and waste gas is then discharged through waste gas filter; Under protection of inert gas, precursor reaches temperature of reaction from room temperature with certain speed, heat-treats, reduce to after the room temperature the hollow plumbago nanostructure.
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 and immerses mixture of ice and water in the test tube, 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 the hollow plumbago nanostructure:
Sample is placed an end of vitrified pipe, and vacuumizing also feeds protection of inert gas.High Temperature Furnaces Heating Apparatus is warming up to 700 ℃ of reaction high temperature from room temperature, after reaching temperature of reaction, with the high-temperature zone that vitrified pipe inserts stove, control heat-up rate 200 degrees centigrade minutes
-1, and be incubated 30 minutes, and extract vitrified pipe subsequently out, place the room temperature environment air cooling to room temperature, repeat above process 2 times, to improve transformation efficiency.Promptly get the hollow plumbago nanostructure.
Removing of step 3, remainder catalyst:
(1) the hollow plumbago nanostructure 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 80 ℃ 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 graphite-structure hollow Nano carbon balls of removing remainder catalyst immediately.
Implementation result: at first make the precursor that contains iron particle, get the hollow plumbago nanostructure after the thermal treatment, remainder catalyst is fallen in last pickling, wherein get the hollow plumbago nanostructure after the thermal treatment and account for cumulative volume 30%, after removing remainder catalyst, graphite-structure hollow Nano carbon balls diameter Distribution is at two scope 3～8nm (accounting for volume fraction 30%) and 25～50nm (accounting for volume fraction 70%), its wall thickness of 3～8nm is below 2 nanometers, its wall thickness of 25～50nm is the 3-6 nanometer, the graphite number of plies is 1～20 layer.
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 25: 9, mixed gas is fed iron carbonyl liquid take catalyzer formation reactant gases out of, liquid is placed on and immerses mixture of ice and water in the test tube, makes iron carbonyl liquid remain 0 ℃; The main reactor temperature is risen to 850 ℃, 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 the hollow plumbago nanostructure:
Sample is placed an end of vitrified pipe, and vacuumizing also feeds protection of inert gas.High Temperature Furnaces Heating Apparatus is warming up to 950 ℃ of reaction high temperature from room temperature, after reaching temperature of reaction, with the high-temperature zone that vitrified pipe inserts stove, control heat-up rate 1500 ℃ minutes
-1, and be incubated 5 minutes, and extract pottery subsequently out and place the room temperature environment air cooling to room temperature, repeat above process 4 times, to improve transformation efficiency.Promptly get the hollow plumbago nanostructure.
Removing of step 3, remainder catalyst:
(1) the hollow plumbago nanostructure that step 2 is obtained places pure nitric acid and concentrated hydrochloric acid (37vol%) mixing solutions, and the mixed volume ratio is 25%, places ultrasonator to carry out sonic oscillation this miscellany then, and the time is 2 hours;
(2) mixture after will vibrating is 120 ℃ of heating down, and adds the recirculated water reflux cooling, and the time is 1 hour;
(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 graphite-structure hollow Nano carbon balls of removing remainder catalyst immediately.
Implementation result: at first make the precursor that contains iron particle, get the hollow plumbago nanostructure after the thermal treatment, remainder catalyst is fallen in last pickling, wherein get the hollow plumbago nanostructure after the thermal treatment and account for cumulative volume 80%, after removing remainder catalyst, graphite-structure hollow Nano carbon mean diameter of a ball 6～20nm, its wall thickness is 2～6 nanometers, the graphite number of plies is 6～20 layers, with a small amount of tens nanometer left and right sides heavy wall hollow nano cages.
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 and immerses mixture of ice and water in the test tube, 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 the hollow plumbago nanostructure:
Sample is placed an end of vitrified pipe, and vacuumizing also feeds protection of inert gas.High Temperature Furnaces Heating Apparatus is warming up to 1150 ℃ of reaction high temperature from room temperature, after reaching temperature of reaction, with the high-temperature zone that vitrified pipe inserts stove, control heat-up rate 2000 ℃ minutes
-1, and be incubated 120 minutes, and close the High Temperature Furnaces Heating Apparatus power supply subsequently, make sample cool to room temperature with the furnace, promptly get the hollow plumbago nanostructure.
Removing of step 3, remainder catalyst:
(1) the hollow plumbago nanostructure that step 2 is obtained places pure nitric acid and concentrated hydrochloric acid (37vol%) mixing solutions, and the mixed volume ratio is 5%, places ultrasonator to carry out sonic oscillation this miscellany then, and the time is 0.5 hour;
(2) mixture after will vibrating is 60 ℃ 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 graphite-structure hollow Nano carbon balls of removing remainder catalyst immediately.
Implementation result: at first make the precursor that contains iron particle, get the hollow plumbago nanostructure after the thermal treatment, remainder catalyst is fallen in last pickling, wherein get the hollow plumbago nanostructure after the thermal treatment and account for cumulative volume 70%, after removing remainder catalyst, graphite-structure hollow Nano carbon mean diameter of a ball 3～10nm, its wall thickness is below 2 nanometers, the graphite number of plies is 1～5 layer, with a small amount of diameter tens nanometer left and right sides heavy wall hollow nano cages.
Claims (9)
1. one kind in the solid-state method for preparing down the graphite-structure hollow Nano carbon balls, it is characterized in that, is divided into three steps:
Step 1, preparation have the amorphous carbon precursor of catalyzer:
Rare gas element and acetylene gas are mixed, the iron carbonyl liquid that the mixed gas feeding is 0 ℃ is taken catalyzer out of and is formed reactant gases, it is that react in 550-850 ℃ reactor high temperature district through excess temperature that reactant gases is imported the main reactor top, has obtained the equally distributed amorphous carbon precursor of iron catalyst particle in main reactor bottoms collector continuously;
Step 2, thermal treatment precursor prepare the hollow plumbago nanostructure:
Sample is placed sealing one end of vitrified pipe, vacuumizing also feeds protection of inert gas, High Temperature Furnaces Heating Apparatus is warming up to temperature of reaction 700-1150 ℃ from room temperature, after reaching temperature of reaction, with the high-temperature zone that vitrified pipe inserts stove, the control heat-up rate, cool to room temperature after the insulation with the furnace, perhaps extract the vitrified pipe air cooling out to room temperature, repeat above process, promptly get pattern controllable hollow Nano graphite structure;
Removing of step 3, remainder catalyst:
(1) hollow nano cages that step 2 is obtained places pure nitric acid and concentrated hydrochloric acid mixing solutions, 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 graphite-structure hollow Nano carbon balls of removing remainder catalyst immediately.
2. the solid-state method that prepare down the graphite-structure hollow Nano carbon balls according to claim 1 is characterized in that, in the step 1, with rare gas element and acetylene ratio control 100: 1-25: feed iron carbonyl liquid between 9 and take catalyzer formation reactant gases out of.
3. according to claim 1 or the 2 described solid-state methods that prepare the graphite-structure hollow Nano carbon balls down, it is characterized in that in the step 1, described rare gas element flow velocity is the 10-60 liters per hour
-1Described acetylene gas flow velocity is a 10-60 milliliter minute
-1
4. the solid-state method for preparing the graphite-structure hollow Nano carbon balls down according to claim 1 is characterized in that having the amorphous carbon precursor of catalyzer to be warming up to 550-850 ℃.
5. the solid-state method for preparing the graphite-structure hollow Nano carbon balls down according to claim 1 is characterized in that in the step 2, the heat-up rate scope was at 200-2000 ℃ minute
-1
6. according to claim 1 or the 5 described solid-state methods that prepare the graphite-structure hollow Nano carbon balls down, it is characterized in that, in the step 2, in the temperature of reaction soaking time is 5-120 minute, after soaking time arrives, make sample cool to room temperature with the furnace, perhaps extract vitrified pipe immediately out, place the room temperature environment air cooling to room temperature.
7. the solid-state method of graphite-structure hollow Nano carbon balls down according to claim 1 is characterized in that the process of step 2 repeats 0-4 time.
8. the solid-state method for preparing the graphite-structure hollow Nano carbon balls down according to claim 1, it is characterized in that, in the step 3, hollow plumbago nanostructure after the thermal treatment places pure nitric acid and concentrated hydrochloric acid mixing solutions, mixed volume is than being 0-25%, carry out sonic oscillation then, the time is 0.5～3 hour.
9. according to claim 1 or the 8 described solid-state methods that prepare the graphite-structure hollow Nano carbon balls down, it is characterized in that in the step 3, the mixture after the vibration is heated down at 60-120 ℃, and add the recirculated water reflux cooling, the time is 1～6 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101585531B (en) * | 2009-06-18 | 2010-12-08 | 上海交通大学 | Preparation method of carbon nano cage |
| CN104167552B (en) * | 2013-05-20 | 2016-08-03 | 北京化工大学 | A kind of level aggregated(particle) structure Graphene cage and preparation method thereof |
| CN103754865B (en) * | 2014-01-13 | 2016-08-17 | 深圳市贝特瑞新能源材料股份有限公司 | The preparation method of village hollowing graphite material and prepared village hollowing graphite material thereof |
| CN106006617B (en) * | 2016-05-25 | 2018-04-13 | 广东石油化工学院 | A kind of preparation method and applications of graphene hollow nano cages |
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| CN1438174A (en) * | 2003-03-27 | 2003-08-27 | 上海交通大学 | Carbon nano hollow-ball and its making method |
| CN1583552A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Method for mass preparing hollow nanometer carbon cages |
| CN1587032A (en) * | 2004-09-14 | 2005-03-02 | 武汉大学 | Hollow charcoal and its synthetic method and use |
| CN1785801A (en) * | 2005-11-10 | 2006-06-14 | 上海交通大学 | Method of large quantity preparing hollow carbon nano-cage |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438174A (en) * | 2003-03-27 | 2003-08-27 | 上海交通大学 | Carbon nano hollow-ball and its making method |
| CN1583552A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Method for mass preparing hollow nanometer carbon cages |
| CN1587032A (en) * | 2004-09-14 | 2005-03-02 | 武汉大学 | Hollow charcoal and its synthetic method and use |
| CN1785801A (en) * | 2005-11-10 | 2006-06-14 | 上海交通大学 | Method of large quantity preparing hollow carbon nano-cage |
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