CN101531361B - Method for preparing Y-shaped carbon nano tube by taking dimethyl sulfide as carbon source - Google Patents
Method for preparing Y-shaped carbon nano tube by taking dimethyl sulfide as carbon source Download PDFInfo
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- CN101531361B CN101531361B CN2009100738927A CN200910073892A CN101531361B CN 101531361 B CN101531361 B CN 101531361B CN 2009100738927 A CN2009100738927 A CN 2009100738927A CN 200910073892 A CN200910073892 A CN 200910073892A CN 101531361 B CN101531361 B CN 101531361B
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Abstract
The invention relates to a method for preparing a Y-shaped carbon nano tube by taking dimethyl sulfide as the carbon source, which is characterized in that in the method, dimethyl sulfide is taken as the carbon source; cobalt nitrate and magnesium nitrate are taken as catalysts; deionized water is taken as a washing agent and a cleaner; dilute hydrochloric acid is taken as a centrifugal cleaner; anhydrous alcohol is taken as a cleaner; hydrogen is taken as carbon source carrier gas and cobalt oxide reducing gas; argon gas is taken as protective gas and a quartz boat is taken as a product growing body. The method comprises the following steps: the catalysts first undergo thermal decomposition reaction and hydrogen reduction and then are placed on the quartz boat; hydrogen is taken as the carbon source carrier gas; the dimethyl sulfide is input into a quartz tube and undergoes shape transformation, vapor deposition and product growth at the temperature of 1000 DEG C under the protection of argon gas and in the presence of catalysts from liquid state, gas state to solid state to generate the black hollow Y-shaped carbon nano tube. The method features short process flow and the product has regular morphology, high purity and stable chemical and physical property, diameter of 50-60nm, hollow diameter of 30-40nm, maximum length of 30000nm, carbon content of 98.9%, productivity as high as 83%.
Description
Technical field
The present invention relates to a kind of is the method that carbon source prepares Y type carbon nanotube with the dimethyl sulphide, belongs to the technical field of organic compound carbon material synthesizing carbon nanotubes.
Background technology
Carbon nanotube has unique hollow structure, shows excellent character at aspects such as electricity, calorifics, optics, mechanics, makes it have broad prospect of application at aspects such as high performance composite, catalytic material, an emission nano-device, transmitters.
Y shape carbon nanotube outer shape is as English alphabet Y, it is except the excellent properties with common carbon nanotube, the character that has more self uniqueness with use part, for example, it can be used as nanotube switch or transistor, be applied on the nano electron device, Y shape carbon nanotube has multidisciplinary potential research using value, belongs to front line science.
At present, the method for preparing Y shape carbon pipe has: laser evaporation method, arc discharge method and chemical Vapor deposition process etc.; The normal carbon source presoma that uses has: acetylene, methane, ethanol, ethene and toluene; Though these methods can realize the preparation of Y type carbon nanotube, but exist some defectives and deficiency in the preparation process, such as, the equipment complexity that has, technical process are grown, are difficult to grasp and control, the product morphology change that has is big, inhomogeneous, product purity is low, yield is low, the cost height can not satisfy the industrial circle needs.
Summary of the invention
Goal of the invention
Purpose of the present invention is exactly at disadvantages of background technology, adopt new carbon source and preparation method, with the dimethyl sulphide is carbon source, with Xiao Suangu, magnesium nitrate is catalyzer, adopt high temperature gas phase scission reaction to generate Y shape carbon nanotube, with production yield rate, purity and the chemical physics performance that increases substantially Y type carbon nanotube.
Technical scheme
The chemical substance that the present invention uses is dimethyl sulphide, magnesium nitrate, Xiao Suangu, hydrochloric acid, argon gas, hydrogen, deionized water, dehydrated alcohol, and its combination consumption is as follows: with milliliter, gram, centimetre
3Be measure unit
Dimethyl sulphide: C
2H
6S 200ml ± 10ml
Xiao Suangu: Co (NO
3)
2100g ± 1g
Magnesium nitrate: Mg (NO
3)
2100g ± 1g
Hydrochloric acid: HCL 500ml ± 10ml
Dehydrated alcohol: CH
3CH
2OH 500ml ± 10ml
Deionized water: H
2O 10000ml ± 10ml
Hydrogen: H
2300000cm
3± 100cm
3
Argon gas: Ar 500000cm
3± 100cm
3
The preparation method is as follows:
(1), selected raw chemical material
To carry out selectedly to preparing required chemical substance, and carry out the control of purity and precision:
Dimethyl sulphide: liquid liquid 99.0%
Xiao Suangu: solid-state solid 98.0%
Magnesium nitrate: solid-state solid 98.0%
Hydrochloric acid: liquid strength of fluid 10%
Dehydrated alcohol: liquid liquid 99.7%
Deionized water: liquid liquid 99.7%
Hydrogen: gaseous state gas 95%
Argon gas: gaseous state gas 95%
(2), clean silica tube
With deionized water 500ml lavation, scrub the silica tube inwall, make its cleaning, clean two-port with dehydrated alcohol again, dry after the cleaning;
(3), ultrasonic cleaning quartz boat
Quartz boat is placed beaker, add dehydrated alcohol 100ml, place ultrasonic cleaner then, ultrasonic cleaning 15min;
(4), drying treatment quartz boat
Place loft drier dry quartz boat after the ultrasonic cleaning, drying temperature is 70 ℃, and be 25min time of drying;
(5), synthetic catalyst
1. Xiao Suangu 3g, magnesium nitrate 10g are mixed, grind 5min, both are mixed, become: Xiao Suangu+magnesium nitrate mixture with agate mortar;
2. thermal decomposition process: the Xiao Suangu+magnesium nitrate mixture that grinds is placed beaker, put into process furnace then, carry out thermal decomposition process, heat decomposition temperature is 600 ℃ ± 5 ℃, time 120min ± 10min, and chemical heat decomposition reaction equation is:
Cool to 20 ℃ ± 3 ℃ then with the furnace;
3. thermal reduction is handled: the process furnace that the cobalt oxide+magnesia mixture after the thermolysis is put into hydrogen atmosphere carries out reduction reaction, 600 ℃ ± 5 ℃ of reduction temperatures, and the hydrogen input speed is 100cm
3/ min, time 60min ± 5min, the chemical reduction reaction equation is:
Cool to 20 ℃ ± 3 ℃ then with the furnace;
The reduction rear catalyst be: cobalt+magnesium oxide promptly: Co+MgO
4. with the product collection of reduction reaction, be needed catalyzer solid state powder;
(6), preparation Y shape carbon nanotube in the tube type high-temperature furnace
1. catalyst fines is placed quartz boat;
The quartz boat that 2. catalyzer will the be housed silica tube middle part high temperature section of packing into;
3. with portion's shutoff about silica tube, left part inserts tunger tube and hydrogen pipe, and right part inserts escape pipe;
4. the dimethyl sulphide container bottle is installed on hydrogen pipeline;
Liquid dimethyl thioether 100ml ± 5ml is added in the water white Glass Containers bottle, the container bottle that dimethyl sulphide is housed is inserted between two T-valve on the hydrogen pipe, left side T-valve connects hydrogen flowing quantity and takes into account hydrogen cylinder, the right T-valve connects the hydrogen pipe and stretches in the silica tube, by two T-valve, regulate the input period and the input of dimethyl sulphide;
5. open argon bottle, import argon gas in silica tube, the argon gas input speed is 1700cm
3/ min, be 15min input time, drives away obnoxious flavour in the silica tube, and discharged by escape pipe;
6. open hydrogen cylinder, and regulate two T-valve, directly import hydrogen in silica tube, the hydrogen input speed is 100cm
3/ min;
7. open tube type high-temperature furnace, make its intensification, rise to 1000 ℃ ± 5 ℃ by 20 ℃ ± 3 ℃, heat-up rate is 15 ℃/min;
8. regulate two T-valve, in silica tube, import hydrogen+dimethyl sulphide, dimethyl sulphide in the container bottle generation steam that evaporates under hydrogen drives, is imported in the silica tube with hydrogen, be 15min ± 1min input time, dimethyl sulphide carries out scission reaction under 1000 ℃ ± 5 ℃ states, filling decomposition in the quartz boat of catalyzer, growth, generate Y type carbon nanotube, the decomposition reaction formula is as follows:
In the formula:
C: carbon
H
2S: hydrogen sulfide
CH
4: methane
9. furnace cooling
After the decomposition reaction is finished, close tube type high-temperature furnace, close hydrogen cylinder, carbon source valve;
Continue the input argon gas, product cools to 20 ℃ ± 3 ℃ with the furnace in the quartz boat, closes argon bottle after the cooling, opens silica tube, takes out quartz boat;
Inventive principle: when the carbon source dimethyl sulphide on granules of catalyst decomposition reaction takes place, can influence the growth activity point of catalyzer, when the growth activity point occurrence positions on the catalyzer changes, the direction of carbon nano-tube is changed, and the repeatedly variation of this growth activity point has impelled the formation of Y type carbon nanotube;
(7), collect product
The carbon nanotube and the catalyst cobalt+magnesium oxide powder that generate in the quartz boat are collected in the beaker;
(8), remove catalyzer with the dilute hydrochloric acid centrifugation
Adding concentration is 10% dilute hydrochloric acid 100ml in the beaker that fills product and catalyzer, place then and carry out centrifugation on the separating centrifuge, separate revolution 2700r/min, disengaging time 15min, catalyst cobalt+magnesium oxide is dissolved in dilute hydrochloric acid, and the product carbon nanotube precipitates in beaker bottom;
Centrifugation repeats five times;
(9), the deionized water ultrasonic cleaning is five times
The product carbon nanotube of centrifugation is placed beaker, add deionized water 100ml, place ultrasonic cleaner then, carry out ultrasonic cleaning, stay product after the cleaning, that is: black, hollow, Y shape carbon nanotube;
Ultrasonic cleaning repeats five times;
(10), vacuum-drying product
Place vacuum drying oven to carry out drying treatment product after the ultrasonic cleaning and beaker, vacuum tightness is 200Pa, 70 ℃ ± 2 ℃ of drying temperatures, and time of drying, 30min ± 2min promptly got final product after the drying, that is: black, hollow, Y shape carbon nanotube;
(11), detect, chemically examine, analyze, characterize
Pattern, composition, purity, structure to the Y shape carbon nanotube produced chemically examined, analysis and characterization;
Detect, analyze with the crystal structure characteristic of x-ray powder diffraction instrument product;
Amplify 100,000 times with field emission scanning electron microscope, product is carried out morphology analysis;
Amplify 300,000 times with high-resolution electron microscope, microstructure of product is analyzed;
Conclusion: the product pattern is black, hollow, Y shape carbon nanotube, and external diameter is 50-60nm, and internal diameter is 30-40nm, and maximum length is 30000nm;
(12), product stores
The black of preparation, hollow, Y shape carbon nanotube are placed water white Glass Containers, and airtight drying, the clean environment of being stored in wants waterproof, protection against the tide, sun-proof, acid-proof alkali salt to corrode 20 ℃ ± 3 ℃ of storing temps, relative humidity≤10%.
The preparation of described Y shape carbon nanotube; be to be carbon source with the dimethyl sulphide; with cobalt+magnesia mixture is catalyzer; with dilute hydrochloric acid is the centrifugation washing composition; with the deionized water is clean-out system, washing composition, is carbon source carrier gas and cobalt oxide reducing gas with hydrogen, is shielding gas with the argon gas; with the dehydrated alcohol is clean-out system, is Y shape carbon nano tube growth matrix with the quartz boat.
The preparation of described Y shape carbon nanotube; in tube type high-temperature furnace, carry out under the heated condition; temperature is since 20 ℃ ± 3 ℃ intensifications; 15 ℃/min of heat-up rate, temperature rises to 1000 ℃ ± 5 ℃, at this temperature constant temperature insulation 15min ± 1min; this period is vapour deposition, modality, product growth period; stop heating then, under argon shield, cool to 20 ℃ ± 3 ℃ with the furnace.
The preparation of described Y shape carbon nanotube, in tube type high-temperature furnace, carry out, it is as follows that tube type high-temperature furnace prepares state: the bottom is a track 9 in High Temperature Furnaces Heating Apparatus 1, on High Temperature Furnaces Heating Apparatus 1 inside rail 9, be the silica tube 2 of scalable turnover, be tube chamber 3 in the silica tube, is high temperature section 4 in the middle part of in the tube chamber 3, about portion be low temperature section 5,6, putting quartz boat 11 in the high temperature section 4 of tube chamber 3, is cobalt+magnesia catalyst 12 on the quartz boat 11; Right part at silica tube 2 is provided with sealing plug 8 and escape pipe 10, is provided with sealing plug 7 at the silica tube left part, and tunger tube 17, hydrogen pipe 26 are set; Tunger tube 17 connects argon flow amount meter 15, tunger tube 16, argon gas valve 14, argon bottle 13; Hydrogen pipe 26 connects T-valve 22, T-valve 22 connects hydrogen pipe 29,30, hydrogen pipe 29 stretches in the container bottle 20, hydrogen pipe 29 mouths of pipe are positioned at dimethyl sulphide liquid 23 tops of container bottle 20, hydrogen pipe 30 left sides connect T-valve 21, connect hydrogen pipe 27 below the T-valve 21, hydrogen pipe 27 stretches in the container bottle 20, its mouth of pipe stretches in the dimethyl sulphide 23, T-valve 21 left parts connect hydrogen pipe 28, hydrogen flowmeter 25, hydrogen pipe 24, hydrogen valve 19, hydrogen cylinder 18, hold carbon source dimethyl sulphide 23 in the container bottle 20; Generate carbon nano tube products on the catalyzer 12 in the quartz boat 11.
Described Y shape carbon nanotube, its pattern are black, hollow, Y shape carbon pipe, and carbon pipe diameter is 50-60nm, and the hollow diameter of carbon pipe is 30-40nm, and carbon pipe maximum length is 30000nm.
Beneficial effect
The present invention compares with background technology has tangible advance; it is to be carbon source with the dimethyl sulphide; with cobalt+magnesium oxide is catalyzer; with the deionized water is washing composition and clean-out system; with dilute hydrochloric acid is the centrifugation washing composition; with the dehydrated alcohol is clean-out system; with hydrogen is carbon source carrier gas and cobalt oxide reducing gas; with the argon gas is shielding gas; with the quartz boat is catalyzer and carbon nano tube growth matrix; earlier catalyzer is put into quartz boat; again quartz boat is placed in the tube type high-temperature furnace; in silica tube, import argon gas; hydrogen; wherein hydrogen is done carrier gas; dimethyl sulphide is inputed in the silica tube; under 1000 ℃ of states of high temperature; under argon shield; under catalyst; in quartz boat, carry out scission reaction; the product growth; form Y shape carbon nanotube, after the cooling, the product in the quartz boat is washed with the dilute hydrochloric acid centrifugation; remove catalyzer; Y shape carbon nanotube is isolated in washing, and this method technical process is short, product pattern rule; Y-shaped; diameter is 50-60nm, and hollow diameter is 30-40nm, and maximum length is 30000nm; the product purity height; carbon content is 98.9%, and productive rate is up to 83%, the stable performance of product chemical physics; can mate with the number of chemical material, be the very good method for preparing Y shape carbon nanotube.
Description of drawings
Fig. 1 is preparation technology's schema
Fig. 2 prepares state graph for tube type high-temperature furnace
Fig. 3 is preparation temperature and time coordinate graph of a relation
Fig. 4 amplifies 100,000 times of stacking states figure for Y shape carbon nanotube field emission scanning electron microscope
Fig. 5 amplifies 300,000 times of shape appearance figures for Y shape carbon nanotube high-resolution electron microscope
Fig. 6 is a Y shape carbon nanotube X ray diffracting spectrum
Attachedly among the figure show, list of numerals is as follows:
1, High Temperature Furnaces Heating Apparatus, 2, silica tube, 3, tube chamber, 4, high temperature section, 5, low temperature section, 6, low temperature section, 7, sealing plug, 8, sealing plug, 9, track, 10, escape pipe, 11, quartz boat, 12, cobalt+magnesia catalyst, 13, argon bottle, 14, the argon gas valve, 15, the argon flow amount meter, 16, tunger tube, 17, tunger tube, 18, hydrogen cylinder, 19, hydrogen valve, 20, Glass Containers, 21, T-valve, 22, T-valve, 23, dimethyl sulphide, 24, the hydrogen pipe, 25, hydrogen flowmeter, 26, the hydrogen pipe, 27, the hydrogen pipe, 28, the hydrogen pipe, 29, the hydrogen pipe, 30, the hydrogen pipe.
Embodiment
The present invention will be further described below in conjunction with accompanying drawing:
Shown in Figure 1, be preparation technology's schema, strictness to carry out set by step, according to the order of sequence operation.
The value for preparing required chemical substance is to determine by the scope that sets in advance, with gram, milliliter, centimetre
3Be measure unit, when industrialization is produced, with kilogram, liter, rice
3Be measure unit.
Silica tube, quartz boat will clean, and keep clean, in case produce side reaction.
It is clean that the beaker that preparation is used, container, agate mortar, agitator, ultrasonic cleaning machine, separating centrifuge etc. all will keep, to prevent to produce by product.
Xiao Suangu+magnesium oxide will grind in advance, carries out pyrolytic decomposition then and handles, and 600 ℃ ± 5 ℃, time 120min ± 10min also will carry out hydrogen reducing and handle, 600 ℃ ± 5 ℃ of temperature, and time 60min ± 5min, purpose is in order to produce cobalt+magnesia catalyst.
Prepare at tube type high-temperature furnace, put the quartz boat that fills catalyzer earlier, connect production well, tunger tube, hydrogen pipe then, import argon gas, hydrogen set by step, dimethyl sulphide urges down at hydrogen, enters the silica tube high temperature section, under 1000 ℃ ± 5 ℃, carry out form transformation, vapour deposition, product growth on the catalyzer in silica tube, each parameter is wanted strict control.
Will isolate catalyzer with dilute hydrochloric acid behind the product collection, use deionized water wash then, last vacuum-drying makes final product.
Shown in Figure 2, for tube type high-temperature furnace prepares state graph, strictness to operate set by step, the order can not put upside down, whole preparation is to carry out under argon shield, hydrogen be carrier gas be again shielding gas.
Shown in Figure 3, be tube type high-temperature furnace temperature and time coordinate graph of a relation, temperature is since 20 ℃ ± 3 ℃ intensifications, and promptly the A point rises to 1000 ℃ ± 5 ℃ with 15 ℃/min speed, and at this temperature constant temperature insulation 15min, promptly the B-C section cools to 20 ℃ then with the furnace, i.e. the D point.
Shown in Figure 4, for product Y shape carbon nanotube amplifies 100,000 times of stacking states figure, among the figure as can be known: Y shape carbon nanotube is irregular cross stacking and arranges ruler units 200nm.
Shown in Figure 5, for product Y shape carbon nanotube high-resolution electron microscope amplifies 300,000 times of shape appearance figures, among the figure as can be known: Y shape is clear, tube wall is regular, hollow obviously, ruler units 200nm.
Shown in Figure 6, be Y shape carbon nanotube diffracted intensity collection of illustrative plates, ordinate zou is a diffracted intensity, X-coordinate is diffraction angle 2 θ, among the figure as can be known: there is a climax at the place at 26.75 ° of angles, corresponding plane C (002), visible Y shape carbon nanotube carbon content height and pure.
Claims (2)
1. one kind is the method that carbon source prepares Y shape carbon nanotube with the dimethyl sulphide, it is characterized in that: the chemical substance of using is dimethyl sulphide, magnesium nitrate, Xiao Suangu, hydrochloric acid, argon gas, hydrogen, deionized water, dehydrated alcohol, and its combination consumption is as follows: with milliliter, gram, centimetre
3Be measure unit
Dimethyl sulphide: C
2H
6S 200ml ± 10ml
Xiao Suangu: Co (NO
3)
2100g ± 1g
Magnesium nitrate: Mg (NO
3)
2100g ± 1g
Hydrochloric acid: HCL 500ml ± 10ml
Dehydrated alcohol: CH
3CH
2OH 500ml ± 10ml
Deionized water: H
2O 10000ml ± 10ml
Hydrogen: H
2300000cm
3± 100cm
3
Argon gas: Ar 500000cm
3± 100cm
3
The preparation method is as follows:
(1), selected raw chemical material
To carry out selectedly to preparing required chemical substance, and carry out the control of purity and precision:
Dimethyl sulphide: liquid liquid 99.0%
Xiao Suangu: solid-state solid 98.0%
Magnesium nitrate: solid-state solid 98.0%
Hydrochloric acid: liquid strength of fluid 10%
Dehydrated alcohol: liquid liquid 99.7%
Deionized water: liquid liquid 99.7%
Hydrogen: gaseous state gas 95%
Argon gas: gaseous state gas 95%
(2), clean silica tube
With deionized water 500ml lavation, scrub the silica tube inwall, make its cleaning, clean two-port with dehydrated alcohol again, dry after the cleaning;
(3), ultrasonic cleaning quartz boat
Quartz boat is placed beaker, add dehydrated alcohol 100ml, place ultrasonic cleaner then, ultrasonic cleaning 15min;
(4), drying treatment quartz boat
Place loft drier dry quartz boat after the ultrasonic cleaning, drying temperature is 70 ℃, and be 25min time of drying;
(5), synthetic catalyst
1. Xiao Suangu 3g, magnesium nitrate 10g are mixed, grind 5min, both are mixed, become: Xiao Suangu+magnesium nitrate mixture with agate mortar;
2. thermal decomposition process: the Xiao Suangu+magnesium nitrate mixture that grinds is placed beaker, put into process furnace then, carry out thermal decomposition process, heat decomposition temperature is 600 ℃ ± 5 ℃, time 120min ± 10min, and chemical heat decomposition reaction equation is:
Cool to 20 ℃ ± 3 ℃ then with the furnace;
3. thermal reduction is handled: the process furnace that the cobalt oxide+magnesia mixture after the thermolysis is put into hydrogen atmosphere carries out reduction reaction, 600 ℃ ± 5 ℃ of reduction temperatures, and the hydrogen input speed is 100cm
3/ min, time 60min ± 5min, the chemical reduction reaction equation is:
Cool to 20 ℃ ± 3 ℃ then with the furnace;
The reduction rear catalyst be: cobalt+magnesium oxide promptly: Co+MgO
4. with the product collection of reduction reaction, be needed catalyzer solid state powder;
(6), preparation Y shape carbon nanotube in the tube type high-temperature furnace
1. catalyst fines is placed quartz boat;
The quartz boat that 2. catalyzer will the be housed silica tube middle part high temperature section of packing into;
3. with portion's shutoff about silica tube, left part inserts tunger tube and hydrogen pipe, and right part inserts escape pipe;
4. the dimethyl sulphide container bottle is installed on hydrogen pipeline;
Liquid dimethyl thioether 100ml ± 5ml is added in the water white Glass Containers bottle, the container bottle that dimethyl sulphide is housed is inserted between two T-valve on the hydrogen pipe, left side T-valve connects hydrogen flowing quantity and takes into account hydrogen cylinder, the right T-valve connects the hydrogen pipe and stretches in the silica tube, by two T-valve, regulate the input period and the input of dimethyl sulphide;
5. open argon bottle, import argon gas in silica tube, the argon gas input speed is 1700cm
3/ min, be 15min input time, drives away obnoxious flavour in the silica tube, and discharged by escape pipe;
6. open hydrogen cylinder, and regulate two T-valve, directly import hydrogen in silica tube, the hydrogen input speed is 100cm
3/ min;
7. open tube type high-temperature furnace, make its intensification, rise to 1000 ℃ ± 5 ℃ by 20 ℃ ± 3 ℃, heat-up rate is 15 ℃/min;
8. regulate two T-valve, in silica tube, import hydrogen+dimethyl sulphide, dimethyl sulphide in the container bottle generation steam that evaporates under hydrogen drives, is imported in the silica tube with hydrogen, be 15min ± 1min input time, dimethyl sulphide carries out scission reaction under 1000 ℃ ± 5 ℃ states, filling decomposition in the quartz boat of catalyzer, growth, generate Y type carbon nanotube, the decomposition reaction formula is as follows:
In the formula:
C: carbon
H
2S: hydrogen sulfide
CH
4: methane
9. furnace cooling
After the decomposition reaction is finished, close tube type high-temperature furnace, close hydrogen cylinder, carbon source valve;
Continue the input argon gas, product cools to 20 ℃ ± 3 ℃ with the furnace in the quartz boat, closes argon bottle after the cooling, opens silica tube, takes out quartz boat;
Inventive principle: when the carbon source dimethyl sulphide on granules of catalyst decomposition reaction takes place, can influence the growth activity point of catalyzer, when the growth activity point occurrence positions on the catalyzer changes, the direction of carbon nano-tube is changed, and the repeatedly variation of this growth activity point has impelled the formation of Y type carbon nanotube;
(7), collect product
The carbon nanotube and the catalyst cobalt+magnesium oxide powder that generate in the quartz boat are collected in the beaker;
(8), remove catalyzer with the dilute hydrochloric acid centrifugation
Adding concentration is 10% dilute hydrochloric acid 100ml in the beaker that fills product and catalyzer, place then and carry out centrifugation on the separating centrifuge, separate revolution 2700r/min, disengaging time 15min, catalyst cobalt+magnesium oxide is dissolved in dilute hydrochloric acid, and the product carbon nanotube precipitates in beaker bottom;
Centrifugation repeats five times;
(9), the deionized water ultrasonic cleaning is five times
The product carbon nanotube of centrifugation is placed beaker, add deionized water 100ml, place ultrasonic cleaner then, carry out ultrasonic cleaning, stay product after the cleaning, that is: black, hollow, Y shape carbon nanotube;
Ultrasonic cleaning repeats five times;
(10), vacuum-drying product
Place vacuum drying oven to carry out drying treatment product after the ultrasonic cleaning and beaker, vacuum tightness is 200Pa, 70 ℃ ± 2 ℃ of drying temperatures, and time of drying, 30min ± 2min promptly got final product after the drying, that is: black, hollow, Y shape carbon nanotube;
(11), detect, chemically examine, analyze, characterize
Pattern, composition, purity, structure to the Y shape carbon nanotube produced chemically examined, analysis and characterization;
Detect, analyze with the crystal structure characteristic of x-ray powder diffraction instrument product;
Amplify 100,000 times with field emission scanning electron microscope, product is carried out morphology analysis;
Amplify 300,000 times with high-resolution electron microscope, microstructure of product is analyzed;
Conclusion: the product pattern is black, hollow, Y shape carbon nanotube, and external diameter is 50-60nm, and internal diameter is 30-40nm, and maximum length is 30000nm;
(12), product stores
The black of preparation, hollow, Y shape carbon nanotube are placed water white Glass Containers, and airtight drying, the clean environment of being stored in wants waterproof, protection against the tide, sun-proof, acid-proof alkali salt to corrode 20 ℃ ± 3 ℃ of storing temps, relative humidity≤10%.
2. according to claim 1 a kind of be the method that carbon source prepares Y shape carbon nanotube with the dimethyl sulphide, it is characterized in that: the preparation of described Y shape carbon nanotube, in tube type high-temperature furnace, carry out, it is as follows that tube type high-temperature furnace prepares state: the bottom is track (9) in High Temperature Furnaces Heating Apparatus (1), upward be the silica tube of scalable turnover (2) at High Temperature Furnaces Heating Apparatus (1) inside rail (9), in the silica tube is tube chamber (3), the middle part is high temperature section (4) in the tube chamber (3), about portion be first, second low temperature section (5,6), put quartz boat (11) in the high temperature section (4) of tube chamber (3), quartz boat (11) is gone up and is cobalt+magnesia catalyst (12); Right part at silica tube (2) is provided with sealing plug (8) and escape pipe (10), is provided with sealing plug (7) at the silica tube left part, and second tunger tube (17), the 6th hydrogen pipe (26) are set; Second tunger tube (17) connects argon flow amount meter (15), first tunger tube (16), argon gas valve (14), argon bottle (13); The 6th hydrogen pipe (26) connects second T-valve (22), second T-valve (22) connects the 3rd, tetrahydrochysene tracheae (29,30), the 3rd hydrogen pipe (29) stretches in the container bottle (20), the 3rd hydrogen pipe (29) mouth of pipe is positioned at dimethyl sulphide liquid (23) top of container bottle (20), tetrahydrochysene tracheae (30) left side connects first T-valve (21), connect the second hydrogen pipe (27) below first T-valve (21), the second hydrogen pipe (27) stretches in the container bottle (20), its mouth of pipe stretches in the dimethyl sulphide (23), first T-valve (21) left part connects the 3rd hydrogen pipe (28), hydrogen flowmeter (25), the first hydrogen pipe (24), hydrogen valve (19), hydrogen cylinder (18) holds carbon source dimethyl sulphide (23) in the container bottle (20); Catalyzer (12) in the quartz boat (11) is gone up and is generated carbon nano tube products.
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| CN102010690A (en) * | 2010-11-04 | 2011-04-13 | 浙江师范大学 | Carbon nanotube composite material filled with ferrous sulfide, preparation method and application thereof |
| CN102145886B (en) * | 2011-05-11 | 2013-11-13 | 浙江师范大学 | Method for preparing branched carbon nano tube by using dimethyl sulphide as carbon source |
| WO2019035659A1 (en) * | 2017-08-16 | 2019-02-21 | 금호석유화학 주식회사 | Rubber composition for tires including carbon nanotubes, and method for producing same |
| CN114887552B (en) * | 2022-05-20 | 2023-03-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Injection structure for preparing carbon nanotube material and application thereof |
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| CN1569623A (en) * | 2004-04-22 | 2005-01-26 | 华中师范大学 | Preparation for composite material with nanometal or metal oxide distributed on surface of carbon nanotube uniformly |
| WO2007092021A2 (en) * | 2005-02-07 | 2007-08-16 | Hyperion Catalysis International, Inc. | Single-walled carbon nanotube catalyst |
| US20070224104A1 (en) * | 2004-02-09 | 2007-09-27 | Kim Young N | Method for the Preparation of Y-Branched Carbon Nanotubes |
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2009
- 2009-03-03 CN CN2009100738927A patent/CN101531361B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070224104A1 (en) * | 2004-02-09 | 2007-09-27 | Kim Young N | Method for the Preparation of Y-Branched Carbon Nanotubes |
| CN1569623A (en) * | 2004-04-22 | 2005-01-26 | 华中师范大学 | Preparation for composite material with nanometal or metal oxide distributed on surface of carbon nanotube uniformly |
| WO2007092021A2 (en) * | 2005-02-07 | 2007-08-16 | Hyperion Catalysis International, Inc. | Single-walled carbon nanotube catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 王晓敏 等.Y-型纳米碳管的HRTEM研究.《电子显微学报》.2005,第24卷(第6期),551-554. * |
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