CN1246220C - Method for mass preparing hollow nanometer carbon cages - Google Patents
Method for mass preparing hollow nanometer carbon cages Download PDFInfo
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- CN1246220C CN1246220C CNB2004100247000A CN200410024700A CN1246220C CN 1246220 C CN1246220 C CN 1246220C CN B2004100247000 A CNB2004100247000 A CN B2004100247000A CN 200410024700 A CN200410024700 A CN 200410024700A CN 1246220 C CN1246220 C CN 1246220C
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Abstract
The present invention relates to a method for preparing hollow nanometer carbon cages in a large scale, which is used for the technical field of nanometer material preparation. Firstly, solid nanometer carbon cages are prepared, metal carbonyl type liquid and low-carbon type organic liquid are uniformly proportioned to obtain a reaction solution which is put in a volumetric flask, a main reactor is heated and is led in with noble gas, the reaction solution is sprayed in from the top of the main reactor by an electronic peristaltic pump, and the solid nanometer carbon cages wrapped with metal particles are obtained in a bottom product collector of the main reactor; then, the hollow nanometer carbon cages are prepared, the obtained solid nanometer carbon cages are arranged in pure nitric acid or a mixed solution of the pure nitric acid and distilled water, a mixture is arranged in an ultrasonator to be oscillated in an ultrasonic way, the oscillated mixture is heated and is cooled in a reflux way by adding circulation water, the mixture is diluted by adding the distilled water until the solution presents the neutrality or approaches to the neutrality, solid matters are deposited by statically placing the mixture, the liquid on the upper part is poured away, and the solution is dried immediately to obtain the hollow nanometer carbon cages. The present invention has the advantages of simple manufacturing process and scale and mass production.
Description
Technical field
The present invention relates to a kind of a large amount of method for preparing nano cages, particularly a kind of a large amount of methods that prepare hollow nano cages.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, has broad application prospects, and this has just determined in the requirement that can reach serialization and mass-producing aspect its preparation.To satisfy this demand.
The preparation method of hollow nano cages has used for reference the preparation method of nano metal composite particle, mainly contains two big classes: physics preparation method and chemical synthesis.Gas phase coacervation, sputtering method, mechanical milling method, plasma method etc. all belong to physics preparation method one class; Chemical synthesis mainly comprises thermal decomposition method, reduction method, UV sputter auxiliary crystallization method etc.Though a few methods such as arc process can directly make hollow nano cages, 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, carries out subsequent disposal then and obtains hollow nano cages.So will prepare hollow nano cages in a large number then at first need obtain a large amount of solid carbon nanocages, and will reach higher purity, could guarantee the quality product of subsequent disposal like this.
Find by literature search, Huaihe Song etc. on " Chemical Physics Letters " (chemical physics communication) 374 (2003) 400-404, deliver " (skin is enclosed with the nanometer Fe of carbon-coating to Large-scale synthesis of carbon-encapsulated iron carbide nanoparticles
3Synthesizing on a large scale of C particle) be mentioned to the nanometer Fe that a kind of a large amount of preparation skin is enclosed with carbon-coating in the literary composition
3The method of C particle, this method places the high pressure steam pot with quantitative reaction raw materials, obtains nanometer Fe through heating
3The C particle.The method that relates in this method can only provide reaction raw materials quantitatively, the carrying out that can't realize continuous preparation process, and kernel is a carbide particle, is difficult for removing in subsequent disposal, thereby its output and end product quality all have been subjected to certain limitation.Say on the traditional sense, chemical Vapor deposition process is a kind of method that serialization is produced that is suitable for, but traditional gas-solid fluidized bed diameter that only can be used for is greater than 30 microns non-carbon class particulate fluidisation preparation process, the process for preparing nano-complex particle for catalytic pyrolysis, owing to monodimension nanometer material and easy bonding can occur, very easily cause production process the fluidisation difficulty and can't normal running.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of a large amount of method for preparing hollow nano cages is proposed, make it by controlling the fluidized state of reactant under the air-flow effect, realization is enclosed with serialization, the production in enormous quantities of the solid carbon nanocages of metallics, with its pickling, obtain crystallization degree height, purity height and the high hollow nano cages of output then.
The present invention is achieved by the following technical solutions, and the inventive method is divided into two steps, and at first a large amount of preparations are enclosed with the solid carbon nanocages of metallics, then the solid carbon nanocages are carried out subsequent disposal, promptly get hollow nano cages.Particular content is as follows:
Step 1, preparation solid carbon nanocages:
With metal carbonyls liquid (iron carbonyl, cobalt-carbonyl, nickle carbonoxide) and low-carbon (LC) class organic liquid (methyl alcohol, ethanol, acetone) by volume 1: 5-1: 50 even proportionings get reaction soln and place volumetric flask; The main reactor temperature is risen to 650-900 ℃, and feed rare gas element, flow velocity is the 16-120 liters per hour
-1Reaction soln is sprayed into by the main reactor top through electronic peristaltic pump, and the speed of spraying into is 6-100 milliliter hour
-1In main reactor bottoms collector, obtain being enclosed with the solid carbon nanocages of metallics.
Step 2, preparation hollow nano cages:
(1) the solid carbon nanocages that step 1 is obtained places pure nitric acid or pure nitric acid and distilled water mixing solutions (V
Acid/ V
Water=1: 1), place ultrasonator to carry out sonic oscillation this miscellany then, the time is 1～3 hour;
(2) mixture after will vibrating is 100-200 ℃ of heating down, and adds the recirculated water reflux cooling;
(3) with gained mixture adding distil water dilution in the above-mentioned steps, be neutral or near neutral until solution, leave standstill then and make the solid matter deposition and outwell upper liquid, oven dry promptly gets the hollow nano cages of removing metallics immediately.
The present invention the protection of rare gas element with carry down; utilize the catalytic effect of transition metal nanoparticles; process chemical vapour deposition in vertical floating catalytic Reaktionsofen; around the nanoparticle that forms, wrap up the graphite carbon-coating; the bag that forms diameter and be 30-45nm is assisted the solid carbon of metallics nanocages is arranged, and carries out subsequent disposal then and removes the kernel metallics, promptly gets hollow nano cages; detect to such an extent that its wall thickness is 3～7nm, the graphite number of plies is 10～20 layers.The device that this method is used is simple, and easy handling is suitable for serialization, industrial and large-scale production.
Transition metal of the present invention does not need carrier as the use of catalyzer, has simplified technology, and helps making the purifying of product; In the preparation process, make full use of the protectiveness of rare gas element and need not to feed hydrogen, reduced the danger of energy consumption and experiment; Catalyzer and carbon source can be provided continuously, and shift out products therefrom, realize mass-producing, large batch of production; Whole apparatus system adjustability is strong, easy handling.
Embodiment
The device that the inventive method adopts comprises volumetric flask, electronic peristaltic pump, vaporizer, gas inlet, gas flow valve, heating resistor stove, main reactor, product collection device, waste gas filter.During enforcement, reaction soln enters into the vaporizer generating gasification by volumetric flask through electronic peristaltic pump, and forms uniformly mixed gas with carrying gas, enters main reactor then under certain speed.In main reactor, reaction raw materials is through decomposition, formation of deposits solid carbon nanocages, and in the product collection bottom of device, waste gas is then discharged through waste gas filter in the effect deposit of carrying gas.
Content and above device below in conjunction with the inventive method provide specific embodiment:
Embodiment one:
Step 1, preparation solid carbon nanocages:
Iron carbonyl liquid and 1: 5 by volume even proportioning of ethanol are got reaction soln and places volumetric flask; The main reactor temperature is risen to 650 ℃, and feed nitrogen, nitrogen flow rate is 16 liters per hours
-1Reaction soln is sprayed into by the main reactor top through electronic peristaltic pump, and the speed of spraying into is 6 milliliters hours
-1In main reactor bottoms collector, obtain being enclosed with the solid carbon nanocages of metallics.
Step 2, preparation hollow nano cages:
(1) the solid carbon nanocages that step 1 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 100 ℃ of heating down, and adds the recirculated water reflux cooling;
(3) with above-mentioned steps gained mixture adding distil water dilution, be neutral or near neutral until solution, leave standstill then and make the solid matter deposition and outwell upper liquid, oven dry promptly gets the hollow nano cages of removing metallics immediately.
Implementation result: at first make the solid carbon nanocages, its kernel is an iron particle, gets hollow nano cages after the processing, and mean diameter 30～45nm, wall thickness are 3～7nm, and the graphite number of plies is 10～20 layers.
Embodiment two:
Step 1, preparation solid carbon nanocages:
Nickle carbonoxide and 1: 5 by volume proportioning of ethanol are got reaction soln and place volumetric flask; The main reactor temperature is risen to 800 ℃, and feed nitrogen, nitrogen flow rate is 120 liters per hours
-1Reaction soln is sprayed into by the main reactor top through electronic peristaltic pump, and the speed of spraying into is 100 milliliters hours
-1In main reactor bottoms collector, obtain being enclosed with the solid carbon nanocages of metallics.
Step 2, preparation hollow nano cages:
(1) the solid carbon nanocages that step 1 is obtained places pure nitric acid and distilled water mixing solutions (V
Acid/ V
Water=1: 1), place ultrasonator to carry out sonic oscillation this miscellany then, the time is 2 hours;
(2) mixture after will vibrating is 150 ℃ of heating down, and adds the recirculated water reflux cooling;
(3) with the dilution of the continuous adding distil water of above-mentioned steps gained mixture, be neutral or near neutral until solution, leave standstill then and make the solid matter deposition and outwell upper liquid, oven dry promptly gets the hollow nano cages of removing metallics immediately.
Implementation result: at first make the solid carbon nanocages, its kernel is a nickel particles, gets hollow nano cages after the processing, and mean diameter 25～40nm, wall thickness are 2～5nm, and the graphite number of plies is 7～15 layers.
Embodiment three:
Step 1, preparation solid carbon nanocages:
Iron carbonyl and 1: 10 by volume even proportioning of acetone are got reaction soln and place volumetric flask; The main reactor temperature is risen to 750 ℃, and feed nitrogen, nitrogen flow rate is 40 liters per hours
-1Reaction soln is sprayed into by the main reactor top through electronic peristaltic pump, and the speed of spraying into is 30 milliliters hours
-1In main reactor bottoms collector, obtain being enclosed with the solid carbon nanocages of metallics.
Step 2, preparation hollow nano cages:
(1) the solid carbon nanocages that step 1 is obtained places pure salpeter solution, places ultrasonator to carry out sonic oscillation this miscellany then, and the time is 3 hours;
(2) mixture after will vibrating is 200 ℃ of heating down, and adds the recirculated water reflux cooling;
(3) with the dilution of the continuous adding distil water of above-mentioned steps gained mixture, be neutral or near neutral until solution, leave standstill then and make the solid matter deposition and outwell upper liquid, oven dry promptly gets the hollow nano cages of removing metallics immediately.
Implementation result: at first make the solid carbon nanocages, its kernel is an iron particle, gets hollow nano cages after the processing, and mean diameter 40～60nm, wall thickness are 5～10nm, and the graphite number of plies is 15～30 layers.
Embodiment four:
Step 1, preparation solid carbon nanocages:
Iron carbonyl and 1: 30 by volume even proportioning of ethanol are got reaction soln and place volumetric flask; The main reactor temperature is risen to 750 ℃, and feed nitrogen, nitrogen flow rate is 80 liters per hours
-1Reaction soln is sprayed into by the main reactor top through electronic peristaltic pump, and the speed of spraying into is 50 milliliters hours
-1In main reactor bottoms collector, obtain being enclosed with the solid carbon nanocages of metallics.
Step 2, preparation hollow nano cages:
(1) the solid carbon nanocages that step 1 is obtained places pure salpeter solution, places ultrasonator to carry out sonic oscillation this miscellany then, and the time is 2 hours;
(2) mixture after will vibrating is 150 ℃ of heating down, and adds the recirculated water reflux cooling;
(3) with the dilution of the continuous adding distil water of gained mixture in the above-mentioned steps, be neutral or near neutral until solution, leave standstill then and make the solid matter deposition and outwell upper liquid, oven dry promptly gets the hollow nano cages of removing metallics immediately.
Implementation result: at first make the solid carbon nanocages, its kernel is an iron particle, gets hollow nano cages after the processing, and mean diameter 35～55nm, wall thickness are 5～10nm, and the graphite number of plies is 15～30 layers.
Embodiment five:
Step 1, preparation solid carbon nanocages:
Cobalt-carbonyl and 1: 10 by volume even proportioning of ethanol are got reaction soln and place volumetric flask; The main reactor temperature is risen to 900 ℃, and feed nitrogen, nitrogen flow rate is 40 liters per hours
-1Reaction soln is sprayed into by the main reactor top through electronic peristaltic pump, and the speed of spraying into is 50 milliliters hours
-1In main reactor bottoms collector, obtain being enclosed with the solid carbon nanocages of metallics.
Step 2, preparation hollow nano cages:
(1) the solid carbon nanocages that step 1 is obtained places pure nitric acid and distilled water mixing solutions (V
Acid/ V
Water=1: 1), place ultrasonator to carry out sonic oscillation this miscellany then, the time is 3 hours;
(2) mixture after will vibrating is 100 ℃ of heating down, and adds the recirculated water reflux cooling;
(3) with the dilution of the continuous adding distil water of gained mixture in the above-mentioned steps, be neutral or near neutral until solution, leave standstill then and make the solid matter deposition and outwell upper liquid, oven dry promptly gets the hollow nano cages of removing metallics immediately.
Implementation result: at first make the solid carbon nanocages, its kernel is a cobalt particle, gets hollow nano cages after the processing, and mean diameter 25～40nm, wall thickness are 3～7nm, and the graphite number of plies is 10～20 layers.
Claims (5)
1, a kind of a large amount of method for preparing hollow nano cages is characterized in that, is divided into two steps, at first a large amount of preparations are enclosed with the solid carbon nanocages of metallics, then the solid carbon nanocages is carried out subsequent disposal, promptly get hollow nano cages, particular content is as follows:
Step 1, preparation solid carbon nanocages:
Metal carbonyls liquid and the even proportioning of low-carbon (LC) class organic liquid are got reaction soln and place volumetric flask, main reactor heats up, and feeding rare gas element, reaction soln is sprayed into by the main reactor top through electronic peristaltic pump, in main reactor bottoms collector, obtain being enclosed with the solid carbon nanocages of metallics;
Step 2, preparation hollow nano cages:
(1) the solid carbon nanocages that step 1 is obtained places pure nitric acid or pure nitric acid and distilled water 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, be neutral or near neutral until solution, leave standstill then and make the solid matter deposition and outwell upper liquid, oven dry promptly gets the hollow nano cages of removing metallics immediately,
Metal carbonyls liquid and low-carbon (LC) class organic liquid are 1 according to volume ratio: 5-1: 50 even proportionings, described metal carbonyls liquid is a kind of in iron carbonyl, cobalt-carbonyl, the nickle carbonoxide, described low-carbon (LC) class organic liquid is a kind of in methyl alcohol, ethanol, the acetone, and main reactor is warming up to 650～900 ℃.
2, a large amount of method for preparing hollow nano cages according to claim 1 is characterized in that, the flow velocity that feeds rare gas element is the 16-120 liters per hour
-1
3, a large amount of method for preparing hollow nano cages according to claim 1 is characterized in that, the reaction soln speed of spraying into is 6-100 milliliter hour
-1
4, a large amount of method for preparing hollow nano cages according to claim 1 is characterized in that, pure nitric acid or pure nitric acid and distilled water V
Acid/ V
Water=1: 1, the miscellany sonic oscillation time is 1～3 hour.
5, a large amount of method for preparing hollow nano cages according to claim 1 is characterized in that, the mixture after the vibration is 100-200 ℃ of heating down.
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| CN110124651B (en) * | 2018-02-09 | 2022-03-04 | 中国石油化工股份有限公司 | Catalyst containing carbon nanocages and used for decomposing hydrogen sulfide, and preparation method and application thereof |
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