CN101704519B - Ammonium halide heat treatment based method for preparing hollow carbon nanocages - Google Patents
Ammonium halide heat treatment based method for preparing hollow carbon nanocages Download PDFInfo
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- CN101704519B CN101704519B CN2009103104783A CN200910310478A CN101704519B CN 101704519 B CN101704519 B CN 101704519B CN 2009103104783 A CN2009103104783 A CN 2009103104783A CN 200910310478 A CN200910310478 A CN 200910310478A CN 101704519 B CN101704519 B CN 101704519B
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Abstract
An ammonium halide heat treatment based method for preparing hollow carbon nanocages belongs to the technical field of nano material preparation and comprises the following steps: mixing inert gases and acetylene gases and introducing the mixed gases into metal carbonyls liquid, then leading the mixture into a reactor and obtaining solid carbon nanocages coated by metal catalyst beads at the tail of the reactor; mixing the ammonium halide and the solid carbon nanocages and then placing the mixture into the reactor, introducing argon or nitrogen into the reactor and carrying out temperature reaction to obtain a nano mixture; and placing the nano mixture into deionized water for ultrasonic vibration and filtration and carrying out drying to obtain the hollow carbon nanocages. The method can effectively remove the metal catalyst beads inside the carbon nanocages, the processing course has little damage to the graphite structures of the carbon nanocages, and the method is characterized by simple process, low cost, zero pollution and large-scale and mass production.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of nano material, specifically is a kind of based on the heat treated hollow nano cages preparation method of ammonium halide.
Background technology
In recent years, carbon nanomaterial more and more comes into one's own because of its actual application value and the concrete manifestation in application.Nano cages is owing to have the particular structure feature thereby have wide application prospect, 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 under the katalysis of transition metal, and these carbon atoms are wrapped in the surface of metallic particles, forms nano cages.The nano cages internal package that this method obtains has granules of catalyst, and the existence of granules of catalyst directly influences the structure and the character of nano cages, its excellent performance can not be found full expression in application, therefore the granules of catalyst of nano cages inside must be removed, just can obtain hollow nano cages truly.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 carbon nanocages (method for preparing nano cages) " literary composition for 43 (2005) the 1667th～1672 pages, introduce a kind of pickling in the literary composition and removed the method for nano cages catalyzer, concrete technology is: at first primary sample was placed 4mol/L nitric acid room temperature treatment 5 hours, being warming up to 120 ℃ then handled 4 hours, at last sample filtering is collected and transferred in the 12mol/L hydrochloric acid and handled tens of hours, can remove the inner most of iron particle of nano cages; The deficiency of this method is that the inner iron particle removal of 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; andApplications (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 present invention is directed to the prior art above shortcomings, provide a kind of based on the heat treated hollow nano cages preparation method of ammonium halide, can effectively remove the metal catalyst particles of nano cages inside, treating processes does not have destruction to the graphite-structure of nano cages, and loss amount is also very little, and method technology of the present invention is simple, cost is low, pollution-free, the most obvious with ammonium chloride thermal treatment advantage especially, be 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 is mixed the feeding metal carbonyls liquid with rare gas element with acetylene gas, import reactor then, obtains being enclosed with the solid carbon nanocages of metal catalyst particles at the afterbody of reactor;
The internal temperature of described reactor is 1000～1300 ℃;
Described rare gas element is argon gas or nitrogen, and its flow velocity is 80～200L/h, and the flow velocity of described acetylene gas is 0.6～6L/h;
Described metal carbonyls liquid is meant: a kind of in liquid iron carbonyl, cobalt-carbonyl or the nickle carbonoxide.
Step 2 is placed in the reactor ammonium halide and solid carbon nanocages are mixed, feeds argon gas or nitrogen and carry out temperature reaction in reactor, obtains nano-mixture;
The mixed ratio of described ammonium halide and solid carbon nanocages is mass ratio 20: 1～4: 1;
Described temperature reaction is meant: temperature of reactor is risen to 300～1000 ℃, be incubated 10～60 minutes;
Described ammonium halide is a kind of in brometo de amonio, ammonium chloride or the ammonium iodide.
Step 3, after nano-mixture placed deionized water for ultrasonic concussion and filtering, drying is handled and is obtained hollow nano cages;
Described nano-mixture places deionized water to be meant: the concentration of nano-mixture greater than 0g/mL smaller or equal to 0.1g/mL.
The present invention is by the inner solid carbon nanocages that includes metal catalyst particles of chemical gaseous phase depositing process preparation, utilize ammonium halide thermal treatment to make metal catalyst particles come out from the nano cages internal divergence, and rapid and ammonium halide or the reaction of its degradation production, utilize ammonium halide and ammonium halide and the water-soluble character of metal catalyst particles resultant of reaction then, excessive ammonium halide and ammonium halide in the reaction and metal catalyst particles resultant of reaction are dissolved in water and filtration, metal catalyst particles is removed, thereby obtains high-purity hollow nano cages.
The present invention can effectively remove the metal catalyst particles of nano cages inside, particularly for the nano cages of some special construction, as has good carbonization structure, nano cages that wall is thicker, or the thin nano cages of graphite linings; By the ratio and the heat treated temperature and time of control nano cages and ammonium halide, can effectively remove the granules of catalyst of nano cages inside, and treating processes there is not destruction to the graphite-structure of nano cages, loss amount is also less; Simultaneously, the inventive method is easy, and cost is low, and is pollution-free, is easy to realize suitability for industrialized production.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
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 130L/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: 4 that iron particulate nano cages and ammonium chloride are contained in the inside of last step preparation, and the feeding nitrogen protection rises to 400 ℃ rapidly with temperature of reactor, and soaking time is 60 minutes;
Biased sample after the ammonium chloride thermal treatment is placed deionized water by 1g/10mL, ultrasonic concussion 10 minutes.Above-mentioned mixing solutions is filtered, washs, collect sample and also place 80 ℃ to dry 3 hours down, promptly obtain hollow nano cages.
Implementation result: the solid carbon nanocages that this group prepares is tangible hollow structure after ammonium chloride thermal treatment, and inner iron particle disappears, and after deionized water filtered, no ammonium chloride and other resultant of reaction 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 1100 ℃.Nitrogen flow rate is 120L/h, and the acetylene flow velocity is 60mL/min.In reactor afterbody product collector, obtain being enclosed with iron particulate nano cages;
It is mixed and place reactor by weight 1: 8 that iron particulate nano cages and ammonium chloride are contained in the inside of last step preparation, and the feeding argon shield rises to 500 ℃ with temperature of reactor, and soaking time is 40 minutes;
Biased sample after the ammonium chloride processing is scattered in the ethanol ultrasonic concussion 10 minutes by 1g/15mL.Above-mentioned mixing solutions is filtered, washs, collect sample and also place 80 ℃ to dry 3 hours down, promptly obtain hollow nano cages.
Implementation result: the solid carbon nanocages that this group prepares is after adding ammonium chloride thermal treatment purifying, and inner iron particle disappears, and does not have ammonium chloride and other resultant of reaction vestige.Iron-holder is 65wt% in the preceding sample of processing, handles back content and is lower than 2wt%.The nano cages structural integrity, mean diameter 20～40nm, wall thickness 2～4nm, the graphite number of plies is 5～10 layers.
Embodiment 3
Nitrogen/acetylene gas mixture flowed through flows to reactor behind the iron carbonyl liquid, and temperature of reactor is 1300 ℃.Nitrogen flow rate is 170L/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: 20 that iron particulate nano cages and ammonium iodide are contained in the inside of last step preparation, and the feeding nitrogen protection rises to 1000 ℃ rapidly with temperature of reactor, soaking time 20 minutes;
Biased sample after the ammonium iodide thermal treatment is scattered in the deionized water ultrasonic concussion 20 minutes by 1g/20mL.Above-mentioned mixing solutions is filtered, washs, collect sample and also place 80 ℃ to dry 3 hours down, promptly obtain removing iron particulate hollow nano cages.
Implementation result: the solid carbon nanocages that this group prepares is after ammonium chloride thermal treatment and deionized water filtration, and inner iron particle disappears, and does not have ammonium chloride and resultant of reaction vestige.Iron-holder 60wt% in the sample before handling, handling the back is 2wt%.The nano cages structural integrity, mean diameter 20～50nm, wall thickness 3～7nm, the graphite number of plies is 10～20 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: 10 that nickel particulate nanocages and ammonium chloride are contained in the inside of last step preparation, and the feeding nitrogen protection rises to 600 ℃ with temperature of reactor, and soaking time is 30 minutes;
Biased sample 1g/10mL after the ammonium chloride processing is placed ethanol, ultrasonic concussion 10 minutes.Above-mentioned mixing solutions is filtered, washs, collect sample and place 80 ℃ to dry 3 hours down, promptly obtain hollow nano cages.
Implementation result: the solid carbon nanocages that this group prepares is behind ammonium chloride thermal treatment purifying, and the interior nickel particle disappears, and does not have ammonium chloride and other resultant of reaction vestige.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 (5)
1. one kind based on the heat treated hollow nano cages preparation method of ammonium halide, it is characterized in that, may further comprise the steps:
Step 1 is mixed the feeding metal carbonyls liquid with rare gas element with acetylene gas, import reactor then, obtains being enclosed with the solid carbon nanocages of metal catalyst particles at the afterbody of reactor;
Step 2 is placed in the reactor ammonium halide and solid carbon nanocages are mixed, feeds argon gas or nitrogen and carry out temperature reaction in reactor, obtains nano-mixture;
Step 3, after nano-mixture placed deionized water for ultrasonic concussion and filtering, drying is handled and is obtained hollow nano cages;
Described metal carbonyls liquid is meant: a kind of in the iron carbonyl of liquid molten, cobalt-carbonyl or the nickle carbonoxide;
The mixed ratio of described ammonium halide and solid carbon nanocages is mass ratio 20: 1～4: 1;
Described temperature reaction is meant: temperature of reactor is risen to 300～1000 ℃, be incubated 10～60 minutes.
2. according to claim 1ly it is characterized in that based on the heat treated hollow nano cages preparation method of ammonium halide the internal temperature of described reactor is 1000～1300 ℃.
3. according to claim 1 based on the heat treated hollow nano cages preparation method of ammonium halide, it is characterized in that, rare gas element is mixed with acetylene gas described in the step 1 feeds metal carbonyls liquid, rare gas element is argon gas or nitrogen, its flow velocity is 80～200L/h, and the flow velocity of acetylene gas is 0.6～6L/h.
4. according to claim 1ly it is characterized in that described ammonium halide is a kind of in brometo de amonio, ammonium chloride or the ammonium iodide based on the heat treated hollow nano cages preparation method of ammonium halide.
5. according to claim 1 based on the heat treated hollow nano cages preparation method of ammonium halide, it is characterized in that described nano-mixture places deionized water to be meant: the concentration of nano-mixture greater than 0g/mL smaller or equal to 0.1g/mL.
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