CN1903711A - Method of preparing carbon nano tube by Ni/RE/Cu catalyst chemical gaseous phase sedimentation - Google Patents

Method of preparing carbon nano tube by Ni/RE/Cu catalyst chemical gaseous phase sedimentation Download PDF

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CN1903711A
CN1903711A CN 200610014782 CN200610014782A CN1903711A CN 1903711 A CN1903711 A CN 1903711A CN 200610014782 CN200610014782 CN 200610014782 CN 200610014782 A CN200610014782 A CN 200610014782A CN 1903711 A CN1903711 A CN 1903711A
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water
carbon nanotube
reaction
catalyst
catalyst precursor
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CN100358802C (en
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赵乃勤
康建立
师春生
杜希文
李家俊
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Tianjin University
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Tianjin University
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Abstract

The present invention discloses a method for preparing carbon nano tube by using Ni/RE/Cu catalyst and making chemical vapor deposition. Said method includes the following steps: adding nickelous nitrate hexahydrate, yttrium nitrate hexahydrate or cerous nitrate hexahydrate and soaked copper powder into deionized water according to a certain ratio to obtain nickelous nitrate solution; adding sodium hydroxide solution in the above-mentioned nickelous nitrate solution to neutralization reaction to obtain Ni(OH)2/Y(OH)3/Cu or Ni(OH)2/Ce(OH)3/Cu ternary colloid, washing, filtering, drying, grinding and calcining said ternary colloid to obtain Ni/Y/Cu or Ni/Ce/Cu catalyst precursor body, placing said precursor body into quartz reaction tube, introducing hydrogen gas to make reduction, then introducing mixed reaction gas to make catalytic fragmentation reaction to obtain mixed powder of carbon nano tube and catalyst, then using concentrated nitric acid to make treatment so as to obtain pure nano carbon tube.

Description

The method for preparing carbon nanotube with the Ni/RE/Cu catalyst chemical gas phase deposition
Technical field
The present invention relates to a kind of method for preparing carbon nanotube with the Ni/RE/Cu catalyst chemical gas phase deposition.The technology of preparing that belongs to carbon nanotube.
Background technology
Carbon nanotube has got most of the attention with its unique and potential structural performance, electrology characteristic and mechanical characteristics since 1991 are found.For example, carbon nanotube can make its electroconductibility be metal, semi-metal or semiconductive by grid structure and the diameter that changes in the carbon nanotube, and as conductor, the electroconductibility of carbon nanotube can be better than copper; The intensity of carbon nanotube is higher more than 100 times than steel approximately, and proportion has only 1/6 of steel; Carbon nanotube also has high toughness simultaneously, and is very soft, so it is considered to following " super fiber ".So carbon nanotube can be widely used in high-density hydrogen storage material, high strength composite, high definition flat pannel display, nanometer apparatus and electromagnet absorbing material etc.
At present, the method for preparing carbon nanotube mainly contains three kinds of catalystic pyrolysis, arc process and laser evaporation methods.Prepare carbon nanotube with catalystic pyrolysis and need use transition metal (Fe, Co, Ni) or its compound as catalyst usually, support of the catalyst mostly is Al 2O 3, Si or SiO 2Deng.Though with Ni/Al 2O 3It is comparatively ripe to do the development of Preparation of Catalyst carbon nanotube, its output height, and the purity height, but the carbon pipe that obtains is owing to must be not suitable for being applied to matrix material through complicated purification step.And with copper powder as the preparing carriers catalyzer, adopt the CVD legal system to be equipped with carbon nanotube then, had not yet to see bibliographical information.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing carbon nanotube with the Ni/RE/Cu catalyst chemical gas phase deposition.This method technological process is simple, and gained carbon nanotube productive rate, purity height are particularly useful for making metal-base composites.
The present invention is achieved by the following technical solutions, a kind ofly prepares the method for carbon nanotube with the Ni/RE/Cu catalyst chemical gas phase deposition, it is characterized in that comprising following process:
1) preparation Ni/RE/Cu catalyst precursor
Described Ni/RE/Cu catalyst precursor is Ni/Y/Cu and Ni/Ce/Cu catalyst precursor.Its preparation process, at first copper powder is handled through soaked in absolute ethyl alcohol in advance, with six water nickelous nitrates, six water Yttrium trinitrates or six water cerous nitrates and soak after copper powder be that 4-40: 0.4-16: 95.6-44 or Ni: Ce: Cu is that 4-40: 0.2-16: 95.8-44 joins that to obtain nickelous nitrate concentration in the deionized water water be 0.025-0.1mol/L solution by mass ratio Ni: Y: Cu, in this solution, pressed six water nickelous nitrates and sodium hydroxide mol ratio 1: 2, with descending to add naoh concentration by the mol ratio stirring in 1: 3 of six water Yttrium trinitrates or six water cerous nitrates and sodium hydroxide is that 0.1-0.5mol/L solution to neutralization reaction finishes, and obtains Ni (OH) 2/ Y (OH) 3/ Cu or Ni (OH) 2/ Ce (OH) 3/ Cu ternary colloid.After washing, filtration, adopt vacuum drying oven that this ternary colloid is dehydrated under 80-150 ℃, grind with agate mortar, and, obtain Ni/Y/Cu or Ni/Ce/Cu catalyst precursor at 300 ℃ of-500 ℃ of temperature lower calcinations.
2) preparation carbon nanotube
Get step 1) gained Ni/Y/Cu or Ni/Ce/Cu catalyst precursor, be layered in the quartz boat, quartz boat is placed flat-temperature zone, crystal reaction tube middle part; Under nitrogen protection, be warming up to 400 ℃-600 ℃; feeding flow velocity carried out reduction reaction 1.5-4 hour for 80-200mL/min hydrogen; feed nitrogen again; temperature is transferred to 500 ℃-700 ℃; volume ratio by nitrogen and reactant gases is that 1-12 feeds nitrogen and reactant gases methane or acetylene then; the flow velocity of mixed gas is that 200-780mL/min carries out catalytic cracking reaction; reaction 0.25h-4h; under nitrogen atmosphere, furnace temperature is reduced to room temperature; obtain the mixed powder of carbon nanotube and catalyzer, handle obtaining pure CNT (carbon nano-tube) then through concentration for the 65-68% concentrated nitric acid.
The inventive method has following characteristics and advantage:
1) Preparation of Catalyst is simple.
2) output of resulting carbon nanotube is big, and quality is good, the purity height.Gained carbon nanotube caliber is 10-20nm, is evenly distributed the tube wall cleaning.
3) because the prepared carbon nanotube of the present invention is to grow on copper powder, so this carbon nanotube is particularly useful for making carbon nano-tube reinforced metal-matrix composite material.
Description of drawings
Fig. 1 is the preceding TEM photo of carbon nanotube purifying of the inventive method preparation
The TEM photo of Fig. 2 after for the carbon nanotube purifying of the inventive method preparation
Embodiment
Embodiment one
Use the 30mL soaked in absolute ethyl alcohol after 12 hours the 8g electrolytic copper powder, be mixed with the 500mL aqueous solution with 7.926g six water nickelous nitrates and 1.723g six water Yttrium trinitrates, then 2.721g sodium hydroxide is mixed with the 150mL aqueous solution, under the room temperature magnetic agitation, dropwise is added drop-wise in the above-mentioned solution, obtain Ni (OH) 2/ Y (OH) 3/ Cu ternary colloid; With the ternary colloid with deionized water wash, filter paper filtering, adopt vacuum drying oven under 80 ℃, to dehydrate, grind with agate mortar, and under 350 ℃ of nitrogen protections, calcine 2h, obtain the Ni/Y/Cu catalyst precursor.Get the 0.5gNi/Y/Cu catalyst precursor then; be warming up to 500 ℃ under the nitrogen protection; stop nitrogen; feed hydrogen and reduce, hydrogen flow rate is 200mL/min, behind the maintenance 1.5h; turn off hydrogen and feed nitrogen and methane blended gas (nitrogen flow rate 420mL/min; methane flow rate is 60mL/min) reaction 1h turn off gas mixture, furnace temperature is chilled to room temperature under the nitrogen protection, obtains the mixed powder of carbon nanotube and catalyzer.Then mixed powder being put into 20mL concentration is that deionized water wash, filtration obtained pure carbon nanotube after the 65-68% concentrated nitric acid soaked 5h.
Embodiment two
Use the 30mL soaked in absolute ethyl alcohol after a few hours the 17.8g electrolytic copper powder, be mixed with the 681mL aqueous solution with 9.908g six water nickelous nitrates and 0.862g six water Yttrium trinitrates, then 2.906g sodium hydroxide is mixed with the 784mL aqueous solution, under magnetic agitation, dropwise is added drop-wise in the above-mentioned solution, obtain Ni (OH) 2/ Y (OH) 3/ Cu ternary colloid; The ternary colloid is washed, filters, adopt vacuum drying oven under 100 ℃, to dehydrate, grind with agate mortar, and under 400 ℃ of nitrogen protections, calcine 2h, obtain the Ni/Y/Cu catalyst precursor.Get the 0.5gNi/Y/Cu catalyst precursor then, be warming up to 500 ℃ under the nitrogen protection, stop nitrogen, feed hydrogen and reduce, hydrogen flow rate is 100mL/min.After keeping 2h, turn off that hydrogen feeds nitrogen and methane blended gas (nitrogen flow rate 400mL/min, methane flow rate is 100mL/min) reaction 1h turns off gas mixture, furnace temperature is chilled to room temperature under the nitrogen protection, obtains the mixed powder of carbon nanotube and catalyzer.Then mixed powder is put into the 20mL concentrated nitric acid and soaked 5h after scouring, filtration, obtain pure carbon nanotube.
Embodiment three
Use the 30mL soaked in absolute ethyl alcohol after a few hours the 8g electrolytic copper powder, be mixed with the 500mL aqueous solution with 7.926g six water nickelous nitrates and 1.24g six water cerous nitrates, then 2.523g sodium hydroxide is mixed with the 300mL aqueous solution, under magnetic agitation, dropwise is added drop-wise in the above-mentioned solution, obtain Ni (OH) 2/ Ce (OH) 3/ Cu ternary colloid; The ternary colloid is washed, filters; adopt vacuum drying oven under 150 ℃, to dehydrate; grind with agate mortar, under nitrogen protection, powder is warming up to 400 ℃ of calcining 2h 300 ℃ of follow-up continuing of insulation 2h earlier then, obtain the Ni/Ce/Cu catalyst precursor.Get the 0.5gNi/Y/Cu catalyst precursor then, be warming up to 500 ℃ under the nitrogen protection, stop nitrogen, feed hydrogen and reduce, hydrogen flow rate is 100mL/min.After keeping 2h, turn off that hydrogen feeds nitrogen and methane blended gas (nitrogen flow rate 720mL/min, methane flow rate is 60mL/min) reaction 1h turns off gas mixture, furnace temperature is chilled to room temperature under the nitrogen protection, obtains the mixed powder of carbon nanotube and catalyzer.Then mixed powder is put into the 20mL concentrated nitric acid and soaked 5h after scouring, filtration, obtain pure carbon nanotube.
Embodiment four
Use the 30mL soaked in absolute ethyl alcohol after a few hours the 8g electrolytic copper powder, be mixed with the 500mL aqueous solution with 7.926g six water nickelous nitrates and 1.723g six water Yttrium trinitrates, then 2.721g sodium hydroxide is mixed with the 300mL aqueous solution, under magnetic agitation, dropwise is added drop-wise in the above-mentioned solution, obtain Ni (OH) 2/ Y (OH) 3/ Cu ternary colloid; The ternary colloid is washed, filters; adopt vacuum drying oven under 80 ℃, to dehydrate; grind with agate mortar, under nitrogen protection, powder is warming up to 400 ℃ of calcining 2h 300 ℃ of follow-up continuing of insulation 2h earlier then, obtain the Ni/Y/Cu catalyst precursor.Get the 0.5gNi/Y/Cu catalyst precursor then, be warming up to 500 ℃ under the nitrogen protection, stop nitrogen, feed hydrogen and reduce, hydrogen flow rate is 100mL/min.After keeping 2h; turn off hydrogen; open nitrogen and continue to be warming up to 650 ℃; feed nitrogen and methane blended gas (nitrogen flow rate 420mL/min then; methane flow rate is 60mL/min) reaction 0.5h turn off gas mixture; furnace temperature is chilled to room temperature under the nitrogen protection, obtains the mixed powder of carbon nanotube and catalyzer.Then mixed powder is put into the 20mL concentrated nitric acid and soaked 5h after scouring, filtration, obtain pure carbon nanotube.

Claims (1)

1. one kind prepares the method for carbon nanotube with the Ni/RE/Cu catalyst chemical gas phase deposition, and described Ni/RE/Cu catalyst precursor is Ni/Y/Cu and Ni/Ce/Cu catalyst precursor, it is characterized in that comprising following process:
1) preparation Ni/RE/Cu catalyst precursor
At first copper powder is handled through soaked in absolute ethyl alcohol in advance, with six water nickelous nitrates, six water Yttrium trinitrates or six water cerous nitrates and soak after copper powder be that 4-40: 0.4-16: 95.6-44 or Ni: Ce: Cu is that 4-40: 0.2-16: 95.8-44 joins that to obtain nickelous nitrate concentration in the deionized water water be 0.025-0.1mol/L solution by mass ratio Ni: Y: Cu, in this solution, pressed six water nickelous nitrates and sodium hydroxide mol ratio 1: 2, with descending to add naoh concentration by the mol ratio stirring in 1: 3 of six water Yttrium trinitrates or six water cerous nitrates and sodium hydroxide is that 0.1-0.5mol/L solution to neutralization reaction finishes, and obtains Ni (OH) 2/ Y (OH) 3/ Cu or Ni (OH) 2/ Ce (OH) 3/ Cu ternary colloid adopts vacuum drying oven that this ternary colloid is dehydrated under 80-150 ℃ after washing, filtration, grinds with agate mortar, and at 300 ℃ of-500 ℃ of temperature lower calcinations, obtains Ni/Y/Cu or Ni/Ce/Cu catalyst precursor;
2) preparation carbon nanotube
Get step 1) gained Ni/Y/Cu or Ni/Ce/Cu catalyst precursor; be layered in the quartz boat; quartz boat is placed flat-temperature zone, crystal reaction tube middle part; under nitrogen protection, be warming up to 400 ℃-600 ℃; feeding flow velocity carried out reduction reaction 1.5-4 hour for 80-200mL/min hydrogen; feed nitrogen again; temperature is transferred to 500 ℃-700 ℃; volume ratio by nitrogen and reactant gases is that 1-12 feeds nitrogen and reactant gases methane or acetylene then; the flow velocity of mixed gas is that 200-780mL/min carries out catalytic cracking reaction; reaction 0.25h-4h; under nitrogen atmosphere, furnace temperature is reduced to room temperature; obtain the mixed powder of carbon nanotube and catalyzer, handle obtaining pure CNT (carbon nano-tube) then through concentration for the 65-68% concentrated nitric acid.
CNB200610014782XA 2006-07-17 2006-07-17 Method of preparing carbon nano tube by Ni/RE/Cu catalyst chemical gaseous phase sedimentation Expired - Fee Related CN100358802C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100443223C (en) * 2007-02-01 2008-12-17 天津大学 Method of producing composite material of carbon nanometer pipe/ nickel/ aluminum improving and toughening alumina radicel
CN102320591A (en) * 2011-06-22 2012-01-18 天津大学 Method for directly growing mesh carbon nanotubes on copper substrate
CN102351164A (en) * 2011-06-22 2012-02-15 天津大学 Method for directly growing vertical nano carbon fiber arrays on copper matrix
CN103754878A (en) * 2014-01-06 2014-04-30 上海交通大学 Method for preparing carbon nano tubes on surfaces of silicon carbide particles through in-situ synthesis
CN105329882A (en) * 2015-12-08 2016-02-17 赵屹坤 Preparation method of carbon nano-tube
CN110589763A (en) * 2019-09-02 2019-12-20 四川普瑞思达科技服务有限公司 Method for preparing hydrogen by catalytic cracking of acetylene
CN110844900A (en) * 2019-11-11 2020-02-28 天津大学 Method for preparing carbon nano tube by taking waste tire as raw material

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CN1186251C (en) * 2003-07-31 2005-01-26 南京大学 Catalyst and method for preparing nanometer carbon tube
CN1544731A (en) * 2003-11-26 2004-11-10 北京理工大学 Catalyst and process for preparing nano carbon fiber and three-dimensional ordered nano carbon fiber packed structure
KR20060002476A (en) * 2004-07-02 2006-01-09 삼성에스디아이 주식회사 Method for preparing catalyst base for manufacturing carbon nano tubes, and method for manufacturing carbon nano tubes employing the same

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100443223C (en) * 2007-02-01 2008-12-17 天津大学 Method of producing composite material of carbon nanometer pipe/ nickel/ aluminum improving and toughening alumina radicel
CN102320591A (en) * 2011-06-22 2012-01-18 天津大学 Method for directly growing mesh carbon nanotubes on copper substrate
CN102351164A (en) * 2011-06-22 2012-02-15 天津大学 Method for directly growing vertical nano carbon fiber arrays on copper matrix
CN102351164B (en) * 2011-06-22 2012-11-14 天津大学 Method for directly growing vertical nano carbon fiber arrays on copper matrix
CN102320591B (en) * 2011-06-22 2013-01-23 天津大学 Method for directly growing mesh carbon nanotubes on copper substrate
CN103754878B (en) * 2014-01-06 2015-10-14 上海交通大学 The method of the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ
CN103754878A (en) * 2014-01-06 2014-04-30 上海交通大学 Method for preparing carbon nano tubes on surfaces of silicon carbide particles through in-situ synthesis
CN105329882A (en) * 2015-12-08 2016-02-17 赵屹坤 Preparation method of carbon nano-tube
CN105329882B (en) * 2015-12-08 2017-05-10 赵屹坤 Preparation method of carbon nano-tube
CN110589763A (en) * 2019-09-02 2019-12-20 四川普瑞思达科技服务有限公司 Method for preparing hydrogen by catalytic cracking of acetylene
CN110589763B (en) * 2019-09-02 2023-02-10 四川普瑞思达科技服务有限公司 Method for preparing hydrogen by catalytic cracking of acetylene
CN110844900A (en) * 2019-11-11 2020-02-28 天津大学 Method for preparing carbon nano tube by taking waste tire as raw material
CN110844900B (en) * 2019-11-11 2022-05-24 天津大学 Method for preparing carbon nano tube by taking waste tire as raw material

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