CN101544365B - Method for preparing hollow carbon nano-cage through iodized thermal treatment - Google Patents
Method for preparing hollow carbon nano-cage through iodized thermal treatment Download PDFInfo
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- CN101544365B CN101544365B CN2009100504500A CN200910050450A CN101544365B CN 101544365 B CN101544365 B CN 101544365B CN 2009100504500 A CN2009100504500 A CN 2009100504500A CN 200910050450 A CN200910050450 A CN 200910050450A CN 101544365 B CN101544365 B CN 101544365B
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Abstract
The invention relates to a method for preparing a hollow carbon nano-cage through iodized thermal treatment, which belongs to the technical field of preparing nanometer materials and comprises the following steps: raising the temperature of a reactor to between 1,000 and 1,300 DEG C so that mixed gas of inert gas and acetylene flows through a metal carbonyl liquid and then flows towards the reactor so as to obtain a solid carbon nano-cage enwrapped with metal catalyst particles, wherein the flow rate of the inert gas is between 100 and 200 liters per hour and the flow rate of the acetylene isbetween 10 and 100 milliliters per minute; mixing iodine with the solid carbon nano-cage obtained in the step one according to the weight ratio of more than or equal to 2:1 and placing the mixture inthe reactor, introducing the inert gas into the reactor, raising the temperature in the reactor to between 400 and 1,000 DEG C, and keeping the temperature for 10 to 60 minutes; and performing ultrasonic vibration on the mixture obtained in the step two in ethanol or acetone for 10 to 30 minutes, filtering the mixture, washing the mixture with deionized water, and drying the mixture at a temperature of 80 DEG C to obtain the hollow carbon nano-cage without the metal catalyst particles. The method can effectively remove the metal catalyst particles in the carbon nano-cage, and has smaller damage to the graphite structure of the carbon nano-cage in the process of the treatment.
Description
Technical field
The present invention relates to a kind of method for preparing hollow nano cages of technical field of nano material, specifically is a kind of method of preparing hollow carbon nano-cage through iodized thermal treatment.
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.There is wide application prospect in nano cages owing to having the particular structure feature, and its outer wall has good carbonization structure, and excellent calorifics, chemical stability and electric property are arranged, and has application potential.The synthetic method of carbon current nanocages is based on chemical Vapor deposition process, and this method at high temperature decomposites active atoms of carbon with carbon-source gas or liquid, and under the katalysis of transition metal, the control reaction conditions is prepared nano cages.This method is inevitably at the inner remaining granules of catalyst of nano cages.The existence of granules of catalyst directly influences the structure and the character of nano cages, and its excellent performance can not be found full expression in application, therefore the granules of catalyst of nano cages inside must be removed.At present, for removing granules of catalyst, method commonly used is broadly divided into physics method and chemical method.The physics method is to utilize the difference of nano cages and granules of catalyst physical property matter, reaches the removal purpose by means of methods such as pyroprocessing, magnetic separation, ultra-sonic dispersion, millipore filtration, centrifugation are separated from each other it.But this method not only productive rate is low, and the part nano cages together is removed with granules of catalyst, and efficient is low, and less granules of catalyst can not be removed fully.Chemical method is according to the chemical property difference between nano cages and the granules of catalyst, react with it with chemical reagent such as acid, alkali, salt, generate the material of volatile or solubility, reach the effect of removing catalyzer, mainly contain methods such as vapour phase oxidation process, liquid phase oxidation, electrochemical oxidation process, intercalation oxidation style.But chemical method is a cost to consume the part nano cages usually, and the nano cages structure deteriorate is serious, and loss amount is big.When nano cages has good carbonization structure and outer wall when thicker, above-mentioned oxidation treatment method can not effectively be removed granules of catalyst; And when its outer wall was thin, its thin graphite linings was easy to all be oxidized away, and can not get the hollow Nano carbon basket structure, and loss is serious.
The prior art document is retrieved discovery, Y.W.Ma etc. are at " Carbon " (carbon), delivered " A practical route to the production of carbonnanocages (method for preparing nano cages) " literary composition for 43 (2005) the 1667th～1672 pages, introduced a kind of pickling in the literary composition and removed the method for nano cages catalyzer, concrete technology is: at first primary sample is placed 4mol/L HNO
3Middle room temperature treatment 5 hours is warming up to 120 ℃ then and handled 4 hours, at last sample filtering is collected and is transferred among the 12mol/L HCl and handled tens of hours, can remove the inner most of iron particle of nano cages; The deficiency of this method is: the inner iron particle removal of this method gained nano cages is not thorough, and too much defective is caused in the generation duct on the nanocages wall; Z.M.Sheng etc. are at " Advanced Materials " (advanced material), delivered " Thin-Walled Carbon Nanocages:Direct Growth; Characterization; and Applications (thin-walled nano cages: directly prepare; performance and application) " literary composition for 20 (2008) the 1071st～1672 pages, introduced the method that a kind of pyroprocessing is aided with magnetic separation and pickling removal granules of catalyst in the literary composition, concrete technology is: at first place alundum tube to charge into argon shield in sample, alundum tube is heated to 1000 ℃～1350 ℃ rapidly, nano cages is carried out 2 hours pyroprocessing; The ultrasonic concussion 0.5 hour in water phase surfactant mixture of sample dispersion after will handling then, on externally-applied magnetic field, left standstill again 3 hours, with iron content particulate nano cages be deposited into the bottom and hollow nano cages is dispersed in the upper solution, the sample filtering in the upper solution is collected.This process repeats repeatedly, with the hollow Nano cage collected in 250 ℃ of atmospheric oxidations 30 minutes, and at 80 ℃ down with chlorohydric acid picklings 2 hours; Filter the nano cages obtain behind the purifying with deionized water at last.The result shows in the nano cages that the iron particle is effectively removed and graphite linings does not wreck, its deficiency is: the method technology of this removal catalyzer is too complicated, major part comprises separated the going out of nano cages of granules of catalyst and can not get effective utilization, and output is extremely low.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method of preparing hollow carbon nano-cage through iodized thermal treatment is provided.The present invention can effectively remove the metal catalyst particles of nano cages inside, and treating processes is less to the graphite-structure destruction of nano cages, and loss amount is also less, and method of the present invention is easy, and cost is low, is easy to realize suitability for industrialized production.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
Step 1, reactor is risen to 1000 ℃～1300 ℃, rare gas element and acetylene gas mixture are flowed through and are flowed to reactor after the metal carbonyls liquid, the rare gas element flow velocity is 100L～200L/h, the acetylene flow velocity is 10ml～100ml/min, obtains being enclosed with the solid carbon nanocages of metal catalyst particles in reactor afterbody product collector;
Step 2, the solid carbon nanocages that iodine and step 1 are obtained feeds rare gas element by weight 〉=2: 1 mixed and place reactor, and temperature of reactor is risen to 400 ℃～1000 ℃, is incubated 10～60 minutes;
Step 3, with the ultrasonic concussion 10～30 minutes in ethanol or acetone of step 2 gained mixture, after filtration, deionized water wash, 80 ℃ of dryings promptly obtain removing the hollow nano cages of metal catalyst particles.
Described rare gas element is argon gas or nitrogen.
In the step 1, described metal carbonyls liquid is a kind of in iron carbonyl liquid, cobalt-carbonyl liquid or the nickle carbonoxide liquid.
In the step 3, the ratio≤1g/10ml of described mixture in ethanol or acetone.
The present invention is by the inner solid carbon nanocages that includes metal catalyst particles of chemical gaseous phase depositing process preparation, utilization adds iodine thermal treatment makes metal catalyst particles come out from the nano cages internal divergence, and rapid and iodine molecule reaction, utilize iodine and iodide to be dissolved in the character of ethanol or acetone solvent then, the iodide of iodine excessive in the reaction and generation are dissolved in ethanol or acetone solvent and filtration, metal catalyst particles is removed, thereby obtains high-purity hollow nano cages.
The present invention has following beneficial effect: the present invention can effectively remove the metal catalyst particles of nano cages inside, particularly for the nano cages of some special construction, as have good carbonization structure, nano cages that wall is thicker, or the thin nano cages of graphite linings; The present invention can effectively remove the granules of catalyst of nano cages inside by the ratio and the heat treated temperature and time of control nano cages and iodine, and treating processes is less to the graphite-structure destruction of nano cages, and loss amount is also less; Simultaneously, method of the present invention is easy, and cost is low, is easy to realize suitability for industrialized production.
Embodiment
Following example will the invention will be further described in conjunction with the accompanying drawings.Present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1
Nitrogen/acetylene gas mixture flowed through flows to reactor behind the iron carbonyl liquid, and temperature of reactor is 1000 ℃, and nitrogen flow rate is 120L/h, and the acetylene flow velocity is 50ml/min, obtains inside and contain iron particulate nano cages in reactor afterbody product collector;
It is mixed and place reactor by weight 1: 8 that iron particulate nanocages and iodine are contained in the inside of last step preparation, and the feeding argon shield rises to 600 ℃ rapidly with temperature of reactor, and soaking time is 30 minutes;
Biased sample after the iodine thermal treatment is placed ethanol by 1g/10ml, ultrasonic concussion 20 minutes.With above-mentioned mixing solutions filter, washing, be scattered in once more and place 80 ℃ of oven dry 3 hours down in the small amount of ethanol, promptly obtain removing the hollow nano cages of granules of catalyst.
Implementation result: the solid carbon nanocages that this group prepares is tangible hollow structure after adding iodine thermal treatment, and inner iron particle disappears, and after ethanol filtered, no iodine and iron iodide compound were residual.Iron-holder is 70wt% (weight percent) in the preceding sample of processing, and content is lower than 1wt% behind the purifying.The nano cages graphite-structure is complete, mean diameter 20～50nm, and wall thickness 2～5nm, the graphite number of plies is 5～15 layers.
Embodiment 2
Nitrogen/acetylene gas mixture flowed through flows to reactor behind the iron carbonyl liquid, and temperature of reactor is 1300 ℃.Nitrogen flow rate is 160L/h, and the acetylene flow velocity is 40ml/min.In reactor afterbody product collector, obtain being enclosed with iron particulate nano cages;
It is mixed and place reactor by weight 1: 10 that iron particulate nano cages and iodine are contained in the inside of last step preparation, and the feeding nitrogen protection rises to 1000 ℃ rapidly with temperature of reactor, soaking time 35 minutes;
The biased sample that will add after the iodine thermal treatment is scattered in the acetone ultrasonic concussion 10 minutes by 1g/12ml.Above-mentioned mixing solutions is filtered, washs, and sample is scattered in small amount of ethanol once more and places 80 ℃ to dry 3 hours down, promptly obtains removing iron particulate hollow nano cages.
Implementation result: the solid carbon nanocages that this group prepares is after adding the filtration of iodine thermal treatment and ethanol, and inner iron particle disappears, and does not have iodine and iron iodide compound vestige.Iron-holder 60wt% in the sample before handling, handling the back is 3wt%.The nano cages structural integrity, mean diameter 20～50nm, wall thickness 3～7nm, the graphite number of plies is 10～20 layers.
Embodiment 3
Nitrogen/acetylene gas mixture flowed through flows to reactor behind the cobalt-carbonyl liquid, and temperature of reactor is 1100 ℃.Nitrogen flow rate is 120L/h, and the acetylene flow velocity is 60ml/min.In reactor afterbody product collector, obtain being enclosed with the nano cages of cobalt granule;
The nanocages and the iodine that the inside of preparation of last step are contained cobalt granule mixed and placed reactor by weight 1: 8, fed argon shield, and temperature of reactor is risen to 800 ℃, and soaking time is 40 minutes;
Biased sample after the iodinate is scattered in the ethanol ultrasonic concussion 10 minutes by 1g/15ml.Above-mentioned mixing solutions is filtered, washs, and sample is scattered in small amount of ethanol once more and places 80 ℃ to dry 3 hours down, promptly obtains hollow nano cages.
Implementation result: the solid carbon nanocages that this group prepares is after adding iodine thermal treatment purifying, and inner cobalt granule disappears, and does not have iodine and the inferior cobalt compound vestige of iodate.Containing the cobalt amount in the sample before handling is 65wt%, and handling back content only is 2wt%.Nano cages structural integrity nano cages mean diameter 20～40nm, wall thickness 2～4nm, the graphite number of plies is 5～10 layers.
Embodiment 4
Nitrogen/acetylene gas mixture flowed through flows to reactor behind the nickle carbonoxide liquid, and temperature of reactor is 1000 ℃.Nitrogen flow rate is 100L/h, and the acetylene flow velocity is 30ml/min.In reactor afterbody product collector, obtain being enclosed with nickel particulate nano cages;
It is mixed and place reactor by weight 1: 6 that nickel particulate nanocages and iodine are contained in the inside of last step preparation, and the feeding nitrogen protection rises to 700 ℃ with temperature of reactor, and soaking time is 50 minutes;
Biased sample 1g/10ml after the iodinate is placed ethanol, ultrasonic concussion 10 minutes.Above-mentioned mixing solutions is filtered, washs, and sample is scattered in ethanol once more and places 80 ℃ to dry 3 hours down, promptly obtains hollow nano cages.
Implementation result: the solid carbon nanocages that this group prepares is behind iodine thermal treatment purifying, and the interior nickel particle disappears, and does not have iodine and the inferior nickel compound vestige of iodate.Nickel content is 60wt% in the preceding sample of processing, and handling back content is 1wt%.The nano cages structural integrity, mean diameter 20～40nm, wall thickness 2～4nm, the graphite number of plies is 5～10 layers.
Claims (3)
1. the method for a preparing hollow carbon nano-cage through iodized thermal treatment is characterized in that, comprises the steps:
Step 1, reactor is risen to 1000 ℃～1300 ℃, rare gas element and acetylene gas mixture are flowed through and are flowed to reactor after the metal carbonyls liquid, the rare gas element flow velocity is 100L～200L/h, the acetylene flow velocity is 10ml～100ml/min, obtains being enclosed with the solid carbon nanocages of metal catalyst particles in reactor afterbody product collector;
Described metal carbonyls liquid is a kind of in iron carbonyl liquid, cobalt-carbonyl liquid or the nickle carbonoxide liquid;
Step 2, the solid carbon nanocages that iodine and step 1 are obtained feeds rare gas element by weight 〉=2: 1 mixed and place reactor, and temperature of reactor is risen to 400 ℃～1000 ℃, is incubated 10～60 minutes;
Step 3, with the ultrasonic concussion 10～30 minutes in ethanol or acetone of step 2 gained mixture, after filtration, deionized water wash, 80 ℃ of dryings promptly obtain removing the hollow nano cages of metal catalyst particles.
2. the method for preparing hollow carbon nano-cage through iodized thermal treatment according to claim 1 is characterized in that, described rare gas element is argon gas or nitrogen.
3. the method for preparing hollow carbon nano-cage through iodized thermal treatment according to claim 1 is characterized in that, in the step 3, and the ratio≤1g/10ml of described mixture in ethanol or acetone.
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| CN102568856A (en) * | 2012-03-14 | 2012-07-11 | 南京大学 | Method for assembling supercapacitor based on hollow 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 |
| CN109809394B (en) * | 2019-03-25 | 2022-04-22 | 青岛超瑞纳米新材料科技有限公司 | Iodine purification device based on carbon nano tube and purification method thereof |
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| WO2002064868A1 (en) * | 2001-02-12 | 2002-08-22 | William Marsh Rice University | Gas-phase process for purifying single-wall carbon nanotubes and compositions thereof |
| 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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| WO2002064868A1 (en) * | 2001-02-12 | 2002-08-22 | William Marsh Rice University | Gas-phase process for purifying single-wall carbon nanotubes and compositions thereof |
| 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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