CN102728414A - Preparation method of catalyst for preparing single-walled carbon nanotube and application of catalyst - Google Patents
Preparation method of catalyst for preparing single-walled carbon nanotube and application of catalyst Download PDFInfo
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- CN102728414A CN102728414A CN2012102334741A CN201210233474A CN102728414A CN 102728414 A CN102728414 A CN 102728414A CN 2012102334741 A CN2012102334741 A CN 2012102334741A CN 201210233474 A CN201210233474 A CN 201210233474A CN 102728414 A CN102728414 A CN 102728414A
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Abstract
The invention discloses a preparation method of a catalyst for preparing a single-walled carbon nanotube and application of the catalyst. The catalyst can be conveniently and effectively attached onto a substrate by depositing according to a spray process; and the single-walled carbon nanotube can be grown. According to the spray process, the preparation method of the catalyst for preparing the single-walled carbon nanotube at large area and low cost is provided, and a method for preparing the catalyst and growing the single-walled carbon nanotube on a substrate with an irregular shape (such as Al2O3 fiber or sand grains with irregular shapes) is also provided, so that the application range of the single-walled carbon nanotube can be widened.
Description
Technical field
The present invention relates to prepare the single wall carbon nano-tube film technical field, particularly a kind of Preparation of catalysts method and utilization thereof that is used to prepare SWCN.
Background technology
CNT is a kind of new material, is found in 1991 by Japanology personnel Iijima.CNT has character such as excellent mechanics, electricity, calorifics.According to the difference of the tube wall graphite number of plies, CNT is divided into single wall, double-walled and multi-walled carbon nano-tubes.SWCN has littler size, in application-specific such as electronic device, has more excellent performance performance than double-walled or multi-walled carbon nano-tubes.
At present, the main method of preparation SWCN is a chemical vapour deposition technique, and it comprises Preparation of Catalyst and carbon nano tube growth two parts.In the stage of Preparation of Catalyst, existing main stream approach comprises vapour deposition processes such as electron beam evaporation plating, magnetron sputtering, and dipping lifts, rotates liquid phase depositions such as coating.The used instrument and equipment of vapour deposition process is complicated, energy consumption is big and production cost is higher.Large-scale industrial production to SWCN is disadvantageous.Liquid phase method is low for equipment requirements, and is with low cost, but also is difficult to obtain the large scale sample with existing method.Simultaneously, because of being subject to catalyst precursor concentration, dip-coating method is difficult for the adjustable catalyst granules of preparation diameter on a large scale.At last, the method for existing liquid phase production catalyst is not suitable for some substrates in irregular shape (such as fiber etc.) preparation catalyst.
Summary of the invention
Goal of the invention of the present invention is the technical deficiency of producing to existing SWCN, and a kind of Preparation of catalysts method that is used to prepare SWCN is provided, and enlarges the Material Used of SWCN.
Further, the method for a kind of advantages of simplicity and high efficiency with this Preparation of Catalyst SWCN is provided.
For realizing the foregoing invention purpose, the technical scheme that the present invention adopts is:
A kind of method for preparing catalyst is provided, and this preparation method carries out through sprayer unit, and said sprayer unit comprises liquid transport device and ultrasonic the atomizing nozzle that connects through pipeline; The preparation process may further comprise the steps:
1) preparing substrate: the organic impurities of removing substrate surface through physics or Chemical cleaning;
2) preparation catalyst solution: the soluble salt that adopts one or more formation in cobalt, iron, nickel, molybdenum, gold, aluminium or the platinum is as raw material; In the soluble salt one or more in the water-soluble or organic solvent, are obtained one or more catalyst precursor solution;
3) ullrasonic spraying is handled: substrate is placed under ultrasonic the atomizing nozzle of sprayer unit;
When step 1) makes a kind of catalyst precursor solution; Above-mentioned catalyst precursor solution is inserted in the liquid transport device of sprayer unit; The pipeline transmission of this catalyst precursor solution process sprayer unit is to ultrasonic atomizing nozzle; Under action of ultrasonic waves, be atomized into atomization gas, be sprayed onto on the substrate by nozzle at last; To pass through the substrate of spraying processing and calcine, calcining heat is 200C-500
oC, calcination time are 1 min-20min, to the soluble salt decomposition, obtain catalyst, and this catalyst is attached on the substrate;
Or when step 2) when making more than one catalyst precursor solution; Choosing wherein a kind of catalyst precursor solution earlier places in the liquid transport device of sprayer unit; The pipeline transmission of this catalyst precursor solution process sprayer unit is to ultrasonic atomizing nozzle; Under action of ultrasonic waves, be atomized into atomization gas, be sprayed onto on the substrate by nozzle at last; To pass through the substrate of spraying processing and calcine,, obtain the preliminary treatment substrate to the soluble salt decomposition; Then the catalyst precursor solution exchange in the liquid transport device is become wherein a kind of in the residual catalyst precursor solution; The pipeline transmission of this catalyst precursor solution process sprayer unit is to ultrasonic atomizing nozzle; Under action of ultrasonic waves, be atomized into atomization gas, be sprayed onto on the preliminary treatment substrate by nozzle at last; The preliminary treatment substrate of handling through spraying is again calcined, decomposed to soluble salt; Until successively or recycling replacing finish; Wherein, calcining heat is 200C-500
oC, calcining total time is 1 min-20min, obtains catalyst, this catalyst is attached on the substrate.
Preferably, the physics of said substrate cleans and is high-temperature calcination; Said Chemical cleaning is that plasma clean or ultraviolet light clean.
Preferably, said substrate is silicon chip, quartz plate, fiber or the irregular polygon grains of sand; The material of the said fiber or the irregular polygon grains of sand is glass, quartz, aluminium oxide or zirconia and composition thereof.
Preferably, the diameter range of the said fiber or the irregular polygon grains of sand is at 10nm-10mm.
Preferably, said catalyst precursor solution metal atomic mass concentration is 10ppm-20%.
Preferably, said organic solvent is the solvent that alcohol, ketone, benzene or cycloalkanes and composition thereof form.
Preferably, the ultrasonic power of said sprayer unit is 1W-5000W, and the sprayed deposit time is 1s-300s.
Preferably, said atomization gas is shaped as point-like, wire, planar, fan-shaped or taper.
Preferably, in the step 3), the nozzle of said sprayer unit or place substrate under the nozzle to carry out two dimension or three-dimensional moving.
A kind of utilization that is used to prepare the catalyst of SWCN prepares SWCN with the substrate that is attached with catalyst through chemical vapour deposition technique.Concrete grammar is following:
Use the method for above-mentioned Preparation of Catalyst SWCN; Carry out through carbon nano-tube growth apparatus in this method; Carbon nano-tube growth apparatus comprises the quartz ampoule that runs through tube furnace, and a termination of said quartz ampoule has mass-flow gas meter, and the other end is connected to vavuum pump; Be connected to valve between said quartz ampoule and the vavuum pump, be connected to vacuum meter between said quartz ampoule and the control valve; In addition, said tube furnace is through the temperature controller heating; It is characterized in that comprising the steps:
The substrate that (1) will be attached with catalyst is put into the centre of quartz ampoule; The open vacuum pump; And the flow that the argon gas in the mass-flow gas meter is set respectively is 10-1000sccm, and the flow of hydrogen is 1-100 sccm, two kinds of gases of input in quartz ampoule; Control valve, thus the pressure in the quartz ampoule regulated;
(2) temperature controller is set: the temperature of tube furnace is raised to 750 ℃ earlier from room temperature; Then be raised to 800 ℃ again from 750 ℃; After this, the temperature of tube furnace remains on 800 ℃; Press like upper type heating tube formula stove, and the pressure in the quartz ampoule remains on 10-120 KPa;
(3) after the tube furnace temperature reaches 800 ℃, wait for to the tube furnace temperature stabilization; Afterwards, stop to import argon gas and hydrogen; Treat that vacuum meter shows that pressure has dropped to 10 Pa when following, in quartz ampoule, import the alcohol gas in the mass-flow gas meter, make it to grow being attached with on the substrate of catalyst, and the flow that this alcohol gas is set is 1-1000sccm; Simultaneously, control valve makes vacuum meter pressure be stabilized in 100Pa-10 KPa, grows;
(4) stop to import alcohol gas; Then, in quartz ampoule, import argon gas, and the flow that argon gas is set is 1-1000 sccm; The closing temperature controller stops to heat tube furnace, and tube furnace is lowered the temperature naturally;
(5) when tube furnace cools to below 200 ℃ naturally, valve-off; When showing quartzy intraductal pressure, vacuum meter reaches 1.0 * 10
5During Pa, close vavuum pump; And stop to import argon gas, and take out through growth substrates, be SWCN; So far, SWCN growth ending.
The present invention has following beneficial effect with respect to prior art:
1) the present invention can prepare catalyst fast, efficiently, on a large scale and carry out carbon nano tube growth through the method for spraying;
2) in the Preparation of catalysts method; Utilization comes on a large scale to regulate and control the characteristics of the component ratio of catalyst alloy to reach the purpose of regulation and control SWCN product structure through the length of spray time; As to test used catalyst be the Co/Mo alloy; Through spray time length, can regulate and control the mass fraction ratio of Co/Mo on a large scale, thus the structure of regulation and control SWCN;
3) in the Preparation of catalysts method, utilize the method for spraying, solve at some out-of-shape substrates (such as Al
2O
3The fiber or the grains of sand in irregular shape) on be convenient to prepare catalyst, thereby enlarge the application of SWCN.
Description of drawings
Fig. 1 is the structure chart of sprayer unit;
Fig. 2 is the carbon nano-tube growth apparatus structure chart;
Fig. 3 is for being substrate with the Si sheet, the sem photograph (scale is 5 microns on the figure) of the SWCN that the spray time of Co:Mo grows out during all for 5s;
Fig. 4 handles the Al that grows out for spraying
2O
3The sem photograph of fibrous carbon nanotube;
Fig. 5 is Al
2O
3Fiber spraying Co/Mo alloy catalyst and carry out carbon nano tube growth after SEM (SEM) figure (scale all is 200 nanometers).
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment goal of the invention of the present invention is done to describe in further detail, embodiment can not give unnecessary details at this one by one, but therefore embodiment of the present invention is not defined in following examples.Unless stated otherwise, the material and the processing method of the present invention's employing are present technique field conventional material and processing method.Embodiment 1
As shown in Figure 1, sprayer unit comprises ultrasonic the atomizing nozzle 3 and liquid transport device 4 that connects through pipeline 2.When the preparation catalyst, catalyst solution places in the liquid transport device 4, and substrate 1 places the below of ultrasonic atomizing nozzle 3.
As shown in Figure 2, carbon nano-tube growth apparatus comprises the quartz ampoule 6 that runs through tube furnace 7, and a termination of quartz ampoule 6 has mass-flow gas meter 5, and the other end is connected to vavuum pump 12; Be connected to valve 11 between quartz ampoule 6 and the vavuum pump 12, be connected to vacuum meter 10 between quartz ampoule 6 and the valve 11; In addition, tube furnace 7 is through temperature controller 8 heating.
Growing high-quality SWCN on silicon chip substrate;
1) preparing substrate: substrate 1 is a silicon chip, and silicon chip is cut into 1cm * 2cm; Clean 5 min through chemical reagent such as acetone, alcohol, deionized waters successively, use nitrogen (N then
2) rifle dries up, and places under the ultraviolet surface processing equipment irradiation 10 min to remove the organic impurities of silicon chip surface at last;
2) preparation catalyst solution: the 0.0169g Cobalt diacetate tetrahydrate is dissolved in obtains Cobalt diacetate tetrahydrate solution in the 50g ethanol; 0.0090g molybdenum acetic acid dimer is dissolved in obtains molybdenum acetic acid dimer solution in the 50g ethanol; And Cobalt diacetate tetrahydrate solution and molybdenum acetic acid dimer solution all carried out sonicated, ultrasonic time is 30 min;
3) ullrasonic spraying is handled: substrate is placed under the nozzle of sprayer unit; Molybdenum acetic acid dimer solution is inserted in the sprayer unit; Press sprayer unit and begin switch; Under the effect of liquid transport device; The pipeline transmission of molybdenum acetic acid dimer solution process sprayer unit is atomized into atomization gas under action of ultrasonic waves to ultrasonic atomizing nozzle, be sprayed onto on the substrate by nozzle at last; Behind the spraying 5s, will pass through the substrate of spraying processing and calcine, calcining heat is 400
oC, calcination time is 5min, makes molybdenum acetic acid dimer resolve into molybdenum oxide (MoO
3);
The substrate that will pass through calcination processing is re-applied under the nozzle, and the catalyst precursor solution exchange in the sprayer unit is the processing of spraying again of Cobalt diacetate tetrahydrate solution; Press sprayer unit and begin switch, under the effect of liquid transport device, the pipeline transmission of Cobalt diacetate tetrahydrate solution process sprayer unit is atomized into atomization gas under action of ultrasonic waves to ultrasonic atomizing nozzle, be sprayed onto on the substrate by nozzle at last; Spraying 5s; To calcine through the substrate of spraying processing again, calcining heat is 400 ℃ again, and calcination time 5 min make Cobalt diacetate tetrahydrate resolve into cobalt oxide (CoO); So far, catalyst completes.
Taking-up is attached with the silicon chip of catalyst, then carries out following steps:
The silicon chip that (1) will be attached with catalyst is put into the centre of quartz ampoule; Open vacuum pump 12; And the flow that the argon gas in the mass-flow gas meter 5 is set respectively is 500 sccm, and the flow of hydrogen is 20 sccm, two kinds of gases of input in quartz ampoule; Control valve 11 makes vacuum meter 10 be shown as 40 Kpa;
(2) temperature controller 8 is set: the temperature of tube furnace 7 is raised to 750 ℃ from room temperature behind 25min; Then, behind 5 min, be raised to 800 ℃ from 750 ℃; After this, the temperature of tube furnace remains on 800 ℃; Press like upper type heating tube formula stove 7;
(3) after tube furnace 7 temperature reach 800 ℃, wait for that 5 min make tube furnace 7 temperature stabilizations; Afterwards, stop to import argon gas and hydrogen; Treat that vacuum meter 10 shows that pressure have dropped to 10 Pa when following, in quartz ampoule 6, import the alcohol gas in the gas mass flow 5, make it on substrate 9, to grow, and the flow that this alcohol gas is set is 500 sccm; Simultaneously, control valve 11 makes vacuum meter 10 pressure be stabilized in 1.4 Kpa, and growth time is 10 min;
(4) behind the growth 10min, stop to import alcohol gas; Then, in quartz ampoule 6, import argon gas, and the flow that argon gas is set is 500 sccm; Closing temperature controller 8 stops to heat tube furnace 7, and tube furnace 7 is lowered the temperature naturally;
(5) when tube furnace 7 cools to below 200 ℃ naturally, valve-off 11; When vacuum meter 10 shows that pressure reaches 1.0 * 10 in the quartz ampoule 6
5During Pa, close vavuum pump 12; And stop to import argon gas, and take out silicon chip through outgrowth, be SWCN; So far, SWCN growth ending.
Silicon chip SWCN advantage and effect: as shown in Figure 3, be substrate with the Si sheet, the sem photograph of the SWCN that the spray time of Co:Mo grows out during all for 5s
Embodiment 2
Present embodiment is except that following characteristics, and other are all identical with embodiment: growing high-quality SWCN on the alumina fibre substrate:
1) preparing substrate: alumina fibre is cut into 1 * 1cm size, alumina fibre is placed 500
oC is annealing 5min down, to remove the impurity of substrate surface;
2) preparation catalyst solution: 0.0169g Cobalt diacetate tetrahydrate and 0.0090g acetic acid molybdenum are dissolved in 50g ethanol carry out sonicated, ultrasonic time is 60 min, subsequently mixed solution is diluted 100 times with ethanol.
3) ullrasonic spraying is handled: substrate is placed under the nozzle of sprayer unit; Molybdenum acetic acid dimer solution is inserted in the sprayer unit; Press sprayer unit and begin switch; Under the effect of liquid transport device; The pipeline transmission of molybdenum acetic acid dimer solution process sprayer unit is atomized into atomization gas under action of ultrasonic waves to ultrasonic atomizing nozzle, be sprayed onto on the substrate by nozzle at last; Behind the spraying 5s, will pass through the substrate of spraying processing and calcine, calcining heat is 400
oC, calcination time is 5min, makes molybdenum acetic acid dimer resolve into molybdenum oxide (MoO
3);
The substrate that will pass through calcination processing is re-applied under the nozzle, and the catalyst precursor solution exchange in the sprayer unit is the processing of spraying again of Cobalt diacetate tetrahydrate solution; Press sprayer unit and begin switch, under the effect of liquid transport device, the pipeline transmission of Cobalt diacetate tetrahydrate solution process sprayer unit is atomized into atomization gas under action of ultrasonic waves to ultrasonic atomizing nozzle, be sprayed onto on the substrate by nozzle at last; Spraying 5s; To calcine through the substrate of spraying processing again, calcining heat is 400 ℃ again, and calcination time 5 min make Cobalt diacetate tetrahydrate resolve into cobalt oxide (CoO); So far, catalyst completes.
Taking-up is attached with the Al of catalyst
2O
3Fiber, then carry out following steps:
(1) will be attached with the Al of catalyst
2O
3Fiber is put into the centre of quartz ampoule; Open vacuum pump 12; And the flow that the argon gas in the mass-flow gas meter 5 is set respectively is 1000 sccm, and the flow of hydrogen is 40 sccm, two kinds of gases of input in quartz ampoule; Control valve 11 makes vacuum meter 10 be shown as 80 Kpa;
(2) temperature controller 8 is set: the temperature of tube furnace 7 is raised to 800 ℃ from room temperature behind 30 min; Then, behind 5min, be raised to 850 ℃ from 800 ℃; After this, the temperature of tube furnace remains on 850 ℃; Press like upper type heating tube formula stove 7;
(3) after tube furnace 7 temperature reach 850 ℃, wait for that 5min makes tube furnace 7 temperature stabilizations; Afterwards, stop to import argon gas and hydrogen; Treat that vacuum meter 10 shows that pressure have dropped to 10 Pa when following, in quartz ampoule 6, import the alcohol gas in the gas mass flow 5, make it on substrate 9, to grow, and the flow that this alcohol gas is set is 1000 sccm; Simultaneously, control valve 11 makes vacuum meter 10 pressure be stabilized in 3.0 Kpa, and growth time is 10 min;
(4) behind growth 10 min, stop to import alcohol gas; Then, in quartz ampoule 6, import argon gas, and the flow that argon gas is set is 1000 sccm; Closing temperature controller 8 stops to heat tube furnace 7, and tube furnace 7 is lowered the temperature naturally;
(5) when tube furnace 7 cools to below 200 ℃ naturally, valve-off 11; When vacuum meter 10 shows that pressure reaches 1.0 * 10 in the quartz ampoule 6
5During Pa, close vavuum pump 12; And stop to import argon gas, and take out through the growth alumina fibre, be SWCN; So far, SWCN growth ending.
The advantage of alumina fibre SWCN and effect:
Fig. 4 handles the Al of growth for spraying
2O
3The sem photograph of fibrous carbon nanotube.Fig. 5 is Al
2O
3Fiber spraying Co/Mo alloy catalyst and carry out carbon nano tube growth after SEM (SEM) figure (scale of Fig. 4 and Fig. 5 all is 200 nanometers).Comparison diagram 4 and Fig. 5 can clearly see one deck CNT of on the fiber that does not originally have CNT, having grown.
The foregoing description is merely preferred embodiment of the present invention, is not to be used for limiting practical range of the present invention.Be that all equalizations of doing according to content of the present invention change and modification, all contained by claim of the present invention scope required for protection.
Claims (10)
1. Preparation of catalysts method that is used to prepare SWCN, this preparation method carries out through sprayer unit, and said sprayer unit comprises liquid transport device and ultrasonic the atomizing nozzle that connects through pipeline; It is characterized in that the preparation process may further comprise the steps:
1) preparing substrate: the organic impurities of removing substrate surface through physics or Chemical cleaning;
2) preparation catalyst solution: the soluble salt that adopts one or more formation in cobalt, iron, nickel, molybdenum, gold, aluminium or the platinum is as raw material; In the soluble salt one or more in the water-soluble or organic solvent, are obtained one or more catalyst precursor solution;
3) ullrasonic spraying is handled: substrate is placed under ultrasonic the atomizing nozzle of sprayer unit;
When step 2) when making a kind of catalyst precursor solution; Above-mentioned catalyst precursor solution is inserted in the liquid transport device of sprayer unit; The pipeline transmission of this catalyst precursor solution process sprayer unit is to ultrasonic atomizing nozzle; Under action of ultrasonic waves, be atomized into atomization gas, be sprayed onto on the substrate by nozzle at last; To pass through the substrate of spraying processing and calcine, calcining heat is 200C-500
oC, calcination time are 1 min-20min, to the soluble salt decomposition, obtain catalyst, and this catalyst is attached on the substrate;
Or when step 2) when making more than one catalyst precursor solution; Choosing wherein a kind of catalyst precursor solution earlier places in the liquid transport device of sprayer unit; The pipeline transmission of this catalyst precursor solution process sprayer unit is to ultrasonic atomizing nozzle; Under action of ultrasonic waves, be atomized into atomization gas, be sprayed onto on the substrate by nozzle at last; To pass through the substrate of spraying processing and calcine,, obtain the preliminary treatment substrate to the soluble salt decomposition; Then the catalyst precursor solution exchange in the liquid transport device is become wherein a kind of in the residual catalyst precursor solution; The pipeline transmission of this catalyst precursor solution process sprayer unit is to ultrasonic atomizing nozzle; Under action of ultrasonic waves, be atomized into atomization gas, be sprayed onto on the preliminary treatment substrate by nozzle at last; The preliminary treatment substrate of handling through spraying is again calcined, decomposed to soluble salt; Until successively or recycling replacing finish; Wherein, calcining heat is 200C-500
oC, calcining total time is 1 min-20min, obtains catalyst, this catalyst is attached on the substrate.
2. the Preparation of catalysts method that is used to prepare SWCN according to claim 1 is characterized in that: the physics of said substrate cleans and is high-temperature calcination; Said Chemical cleaning is that plasma clean or ultraviolet light clean.
3. the Preparation of catalysts method that is used to prepare SWCN according to claim 1 is characterized in that: said substrate is silicon chip, quartz plate, fiber or the irregular polygon grains of sand; The material of the said fiber or the irregular polygon grains of sand is glass, quartz, aluminium oxide or zirconia and composition thereof.
4. the Preparation of catalysts method that is used to prepare SWCN according to claim 3 is characterized in that: the diameter range of the said fiber or the irregular polygon grains of sand is at 10nm-10mm.
5. the Preparation of catalysts method that is used to prepare SWCN according to claim 1 is characterized in that: said catalyst precursor solution metal atomic mass concentration is 10 ppm-20%.
6. the Preparation of catalysts method that is used to prepare SWCN according to claim 1 is characterized in that: said organic solvent is the solvent that alcohol, ketone, benzene or cycloalkanes and composition thereof form.
7. the Preparation of catalysts method that is used to prepare SWCN according to claim 1 is characterized in that: the ultrasonic power of said sprayer unit is 1W-5000W, and the sprayed deposit time is 1s-300s.
8. the Preparation of catalysts method that is used to prepare SWCN according to claim 1 is characterized in that: said atomization gas be shaped as point-like, wire, planar, fan-shaped or taper.
9. according to each described Preparation of catalysts method that is used to prepare SWCN of claim 1-8, it is characterized in that: in the step 3), the nozzle of said sprayer unit or place substrate under the nozzle to carry out two dimension or three-dimensional moving.
10. one kind according to each described utilization that is used to prepare the catalyst of SWCN of claim 1-9, and it is characterized in that: the substrate that will be attached with catalyst prepares SWCN through chemical vapour deposition technique.
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| CN103464220A (en) * | 2013-09-13 | 2013-12-25 | 太原理工大学 | Method for modifying catalyst through ultrasonic atomization |
| CN104071767A (en) * | 2013-03-25 | 2014-10-01 | 苏州捷迪纳米科技有限公司 | Treating method for carbon nanotube growth substrate |
| CN104085892A (en) * | 2014-05-05 | 2014-10-08 | 资兴市硅纳新材有限公司 | Method for preparing silicon naowires by using liquid source misted deposition of catalyst |
| CN107188159A (en) * | 2017-06-01 | 2017-09-22 | 沙冰娟 | A kind of preparation method of array of multi-walled carbon nanotubes |
| CN107683174A (en) * | 2015-06-04 | 2018-02-09 | 克里蒂泰克公司 | Nozzle assembly and its application method |
| CN112408364A (en) * | 2020-11-30 | 2021-02-26 | 青岛科技大学 | Method for preparing carbon nano tube by catalytic pyrolysis of waste thermosetting plastic |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104071767A (en) * | 2013-03-25 | 2014-10-01 | 苏州捷迪纳米科技有限公司 | Treating method for carbon nanotube growth substrate |
| CN103464220A (en) * | 2013-09-13 | 2013-12-25 | 太原理工大学 | Method for modifying catalyst through ultrasonic atomization |
| CN103464220B (en) * | 2013-09-13 | 2015-01-14 | 太原理工大学 | Method for modifying catalyst through ultrasonic atomization |
| CN104085892A (en) * | 2014-05-05 | 2014-10-08 | 资兴市硅纳新材有限公司 | Method for preparing silicon naowires by using liquid source misted deposition of catalyst |
| CN107683174A (en) * | 2015-06-04 | 2018-02-09 | 克里蒂泰克公司 | Nozzle assembly and its application method |
| CN107683174B (en) * | 2015-06-04 | 2021-02-19 | 克里蒂泰克公司 | Nozzle assembly and method of using the same |
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| CN107188159A (en) * | 2017-06-01 | 2017-09-22 | 沙冰娟 | A kind of preparation method of array of multi-walled carbon nanotubes |
| CN112408364A (en) * | 2020-11-30 | 2021-02-26 | 青岛科技大学 | Method for preparing carbon nano tube by catalytic pyrolysis of waste thermosetting plastic |
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Application publication date: 20121017 |