CN100398436C - Method of large quantity preparing hollow carbon nano-cage - Google Patents
Method of large quantity preparing hollow carbon nano-cage Download PDFInfo
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- CN100398436C CN100398436C CNB2005101102130A CN200510110213A CN100398436C CN 100398436 C CN100398436 C CN 100398436C CN B2005101102130 A CNB2005101102130 A CN B2005101102130A CN 200510110213 A CN200510110213 A CN 200510110213A CN 100398436 C CN100398436 C CN 100398436C
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Abstract
The present invention relates to a method for making large quantity of hollow nanometer carbon cages, which is used for the technical field of nanometer material making. The method comprises: firstly making solid nanometer carbon cages; evenly proportioning metallic carbonyl liquid and low-carbon organic liquid to obtain a reaction solution; filling the reaction solution into a volumetric flask; heating a main reactor; introducing inert gas into the main reactor; spraying the reaction solution in with an end sprayer of the main reactor through an electronic peristaltic pump, and the solid nanometer carbon cages wrapping metal particles are obtained in a tail product collector of the main reactor; then, making the hollow nanometer carbon cages; oxidizing the obtained solid nanometer carbon cages with air and putting the solid nanometer carbon cages into pure hydrochloric acid or a mixed solution of the pure hydrochloric acid and distilled water to be oscillated with ultrasonic waves; after oscillation, washing the mixture with deionized water and filtering the mixture until the solution presents neutrality or approaches to the neutrality, then settling the solution to make solid matter deposited, pouring out supernatant fluid, and drying the solution immediately to obtain the hollow nanometer carbon cages. The present invention has the advantages of simple manufacturing process, 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 a large amount of method for preparing hollow nano cages.
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 change 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 through literature search prior art, Sangjin Han etc. is mentioned to a kind of method for preparing hollow nano cages in " Simple Solid-Phase Synthesisof Hollow Graphitic Nanoparticles and their Application to DirectMethanol Fuel Cell Electrodes " (the simple solid phase synthesis of hollow plumbago nano particle and the application aspect methanol fuel cell thereof) literary composition of delivering on " Advanced Materials " (advanced material) 15 (2003) 1922-1925, be about to quantitative reaction raw materials and contain the metal-salt uniform mixing of granules of catalyst in solution, place inert atmosphere to heat then, obtain nano-metal particle/carbon-coating composite particles, this composite particles is placed rare nitric acid liquid and potassium permanganate (KMnO successively
4) in the solution to remove metallic particles and agraphitic carbon, obtain single hollow plumbago nano particle, its specific surface area only is 88m
2G
-1The method that relates in this literary composition can only provide reaction raw materials, the carrying out that can't realize continuous preparation process quantitatively.In addition, the control of sedimentary homogeneity and particle diameter on carrier of the conductivity of carrier and Pt particle is the key factor of preparation fuel-cell catalyst, and this has just determined the importance that carrier is selected.Now, people mainly use activated carbon and multi-walled carbon nano-tubes to deposit platinum as carrier.Activated carbon has higher specific surface area (＞1000m
2G
-1), but its amorphism has determined it to be unfavorable for conduction; Multi-walled carbon nano-tubes degree of graphitization height, thereby conductivity is good, but the lower usually (100～200m of its specific surface area
2G
-1), the two has all restricted its application.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 to overcome deficiency of the prior art, a kind of a large amount of method for preparing hollow nano cages is provided, 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 atmospheric oxidation and 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 present invention prepares the solid carbon nanocages that is enclosed with metallics at first in a large number, then the solid carbon nanocages is carried out subsequent disposal, promptly gets hollow nano cages.The present invention includes following steps:
(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 through the injector of electronic peristaltic pump by main reactor inside, and the speed of spraying into is 6-100 milliliter hour
-1In main reactor afterbody product collector, obtain being enclosed with the solid carbon nanocages of metallics.
(2) preparation hollow nano cages
1. the solid carbon nanocages atmospheric oxidation (300～400 ℃) that step (1) is obtained, the time is 0.5～2 hour;
2. the mixture after will 1. handling through step places pure hydrochloric acid or pure hydrochloric acid and distilled water mixing solutions (V
Acid/ V
Water=1: 1), sonic oscillation 1～3 hour;
3. gained mixture in the above-mentioned steps is added deionized water rinsing, filtration, 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 protection of rare gas element with carry down; utilize the catalytic effect of transition metal nanoparticles; process chemical vapour deposition in horizontal floating catalytic Reaktionsofen; around the nanoparticle that forms, wrap up the graphite carbon-coating; forming diameter is the solid carbon nanocages that is enclosed with metallics of 20-45nm, 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 3～10nm, the graphite number of plies is 10～20 layers.The apparatus structure that this method is used is simple, easy handling, and it is simple to remove the process of kernel metallics, so method is suitable for serialization, industrial and large-scale production.
Transition metal does not need carrier as the use of catalyzer among the present invention, 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; The device of design can provide catalyzer and carbon source continuously, and shifts out products therefrom, realizes mass-producing, large batch of production; Whole apparatus system adjustability is strong, easy handling.
Embodiment
Embodiment one:
(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 main reactor internal spray device through electronic peristaltic pump, and the speed of spraying into is 100 milliliters hours
-1In main reactor afterbody product collector, obtain being enclosed with the solid carbon nanocages of metallics.
(2) preparation hollow nano cages:
1. the solid carbon nanocages that step (1) is obtained is carried out atmospheric oxidation in 400 ℃, and the time is 0.5 hour;
2. the mixture after will 1. handling through step places pure hydrochloric acid solution, sonic oscillation 1 hour;
3. gained mixture in the above-mentioned steps is added deionized water rinsing, filtration, 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: this group parameter at first makes the solid carbon nanocages, and 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 two:
(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 main reactor internal spray device through electronic peristaltic pump, and the speed of spraying into is 50 milliliters hours
-1In main reactor afterbody product collector, obtain being enclosed with the solid carbon nanocages of metallics.
(2) preparation hollow nano cages:
1. the solid carbon nanocages that step (1) is obtained is carried out atmospheric oxidation in 350 ℃, and the time is 1 hour;
2. the mixture after will 1. handling through step places pure hydrochloric acid solution, sonic oscillation 1.5 hours;
3. gained mixture in the above-mentioned steps is added deionized water rinsing, filtration, 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: this group parameter at first makes the solid carbon nanocages, and 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.
Embodiment three:
(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 main reactor internal spray device through electronic peristaltic pump, and the speed of spraying into is 50 milliliters hours
-1In main reactor afterbody product collector, obtain being enclosed with the solid carbon nanocages of metallics.
(2) preparation hollow nano cages:
1. the solid carbon nanocages that step (1) is obtained is carried out atmospheric oxidation in 300 ℃, and the time is 2 hours;
2. the mixture after will 1. handling through step places pure hydrochloric acid and distilled water mixing solutions (V
Acid/ V
Water=1: 1), in the solution, sonic oscillation 1.5 hours;
3. gained mixture in the above-mentioned steps is added deionized water rinsing, filtration, 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: this group parameter at first makes the solid carbon nanocages, and 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:
(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 main reactor internal spray device through electronic peristaltic pump, and the speed of spraying into is 30 milliliters hours
-1In main reactor afterbody product collector, obtain being enclosed with the solid carbon nanocages of metallics.
(2) preparation hollow nano cages:
1. the solid carbon nanocages that step (1) is obtained is carried out atmospheric oxidation in 350 ℃, and the time is 1 hour;
2. the mixture after will 1. handling through step places pure hydrochloric acid solution, sonic oscillation 3 hours;
3. gained mixture in the above-mentioned steps is added deionized water rinsing, filtration, 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: this group parameter at first makes the solid carbon nanocages, and 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:
(1) preparation solid carbon nanocages:
Iron carbonyl liquid and 1: 50 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 main reactor internal spray device through electronic peristaltic pump, and the speed of spraying into is 6 milliliters hours
-1In main reactor afterbody product collector, obtain being enclosed with the solid carbon nanocages of metallics.
(2) preparation hollow nano cages:
1. the solid carbon nanocages that step (1) is obtained is carried out atmospheric oxidation in 350 ℃, and the time is 1 hour;
2. the mixture after will 1. handling through step places pure hydrochloric acid and distilled water mixing solutions (V
Acid/ V
Water=1: 1), in the solution, sonic oscillation 3 hours;
3. gained mixture in the above-mentioned steps is added deionized water rinsing, filtration, 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: this group parameter at first makes the solid carbon nanocages, and 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.
Claims (9)
1. a method for preparing hollow nano cages in a large number is characterized in that, may further comprise the steps:
(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; The main reactor temperature is raise, and feed rare gas element; Reaction soln is sprayed into through the injector of electronic peristaltic pump by main reactor inside, in main reactor afterbody product collector, obtain being enclosed with the solid carbon nanocages of metallics;
Described metal carbonyls liquid is meant a kind of in iron carbonyl, cobalt-carbonyl, the nickle carbonoxide; Described low-carbon (LC) class organic liquid is meant low-carbon alcohol or low-carbon (LC) ketone;
(2) preparation hollow nano cages
1. the solid carbon nanocages atmospheric oxidation that step (1) is obtained;
2. the mixture after will 1. handling through step places pure hydrochloric acid or pure hydrochloric acid and distilled water mixing solutions, sonic oscillation;
3. gained mixture in the above-mentioned steps is added deionized water rinsing, filtration, 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.
2. a large amount of method for preparing hollow nano cages according to claim 1 is characterized in that, the volume ratio of described metal carbonyls liquid and low-carbon (LC) class organic liquid is 1: 5-1: 50.
3. a large amount of method for preparing hollow nano cages according to claim 1 is characterized in that described low-carbon alcohol is meant methyl alcohol or ethanol.
4. a large amount of method for preparing hollow nano cages according to claim 1 is characterized in that described low-carbon (LC) ketone is meant acetone.
5. a large amount of method for preparing hollow nano cages according to claim 1 is characterized in that, in the described step (1), the main reactor temperature rises to 650-900 ℃.
6. a large amount of method for preparing hollow nano cages according to claim 5 is characterized in that, in the described step (1), the flow velocity of rare gas element is the 16-120 liters per hour
-1
7. a large amount of method for preparing hollow nano cages according to claim 5 is characterized in that, in the described step (1), the injector speed of spraying into is 6-100 milliliter hour
-1
8. a large amount of method for preparing hollow nano cages according to claim 1 is characterized in that, in the described step (2), solid carbon nanocages atmospheric oxidation temperature is 300～400 ℃.
9. a large amount of method for preparing hollow nano cages according to claim 8 is characterized in that, in the described step (2), the solid carbon nanocages atmospheric oxidation time is 0.5～2 hour.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372761C (en) * | 2006-06-22 | 2008-03-05 | 上海交通大学 | Method for preparing hollow Nano carbon balls in graphite structure under solid state |
| CN101249958B (en) * | 2008-03-20 | 2010-06-09 | 上海交通大学 | Method for continuous synthesis of a great amount of high specific surface area highly-graphitized carbon nano-cage by bubbling process |
| 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 |
| CN103787305B (en) * | 2014-02-19 | 2015-11-18 | 中国科学院上海硅酸盐研究所 | Combustion method prepares the method for hollow nano cages |
| CN105293468A (en) * | 2015-11-04 | 2016-02-03 | 上海应用技术学院 | Method for efficiently preparing sulphur-doped hollow carbon spheres |
| CN114797797B (en) * | 2022-03-11 | 2023-04-28 | 湖北工业大学 | Preparation method of hollow carbon nano-cage hydrogel adsorption material with anion recognition function |
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| JP2002338220A (en) * | 2001-03-15 | 2002-11-27 | Osaka Gas Co Ltd | Carbon composite including iron compound and method for producing the same |
| US20030165648A1 (en) * | 2002-03-04 | 2003-09-04 | Alex Lobovsky | Composite material comprising oriented carbon nanotubes in a carbon matrix and process for preparing same |
| US20040234444A1 (en) * | 2001-05-15 | 2004-11-25 | Shaffer Milo S P | Synthesis of nanoscaled carbon materials |
| CN1583552A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Method for mass preparing hollow nanometer carbon cages |
| US20050042160A1 (en) * | 2002-03-15 | 2005-02-24 | Osaka Gas Company Limited | Iron-carbon composite, carbonaceous material comprising said iron-carbon composite and process for preparing the same |
| JP2005082830A (en) * | 2003-09-05 | 2005-03-31 | Nissin Kogyo Co Ltd | Carbon fiber composite metallic material and manufacturing method therefor |
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2005
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002338220A (en) * | 2001-03-15 | 2002-11-27 | Osaka Gas Co Ltd | Carbon composite including iron compound and method for producing the same |
| US20040234444A1 (en) * | 2001-05-15 | 2004-11-25 | Shaffer Milo S P | Synthesis of nanoscaled carbon materials |
| US20030165648A1 (en) * | 2002-03-04 | 2003-09-04 | Alex Lobovsky | Composite material comprising oriented carbon nanotubes in a carbon matrix and process for preparing same |
| US20050042160A1 (en) * | 2002-03-15 | 2005-02-24 | Osaka Gas Company Limited | Iron-carbon composite, carbonaceous material comprising said iron-carbon composite and process for preparing the same |
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| 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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