CN1318135C - Catalyst of metallic oxide for preparing nanowall nano carbon pipe and preparation process thereof - Google Patents
Catalyst of metallic oxide for preparing nanowall nano carbon pipe and preparation process thereof Download PDFInfo
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- CN1318135C CN1318135C CNB2005100499010A CN200510049901A CN1318135C CN 1318135 C CN1318135 C CN 1318135C CN B2005100499010 A CNB2005100499010 A CN B2005100499010A CN 200510049901 A CN200510049901 A CN 200510049901A CN 1318135 C CN1318135 C CN 1318135C
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Abstract
The present invention relates to a metallic oxide catalyst and a preparation method thereof for preparing single wall carbon nanotubes. The catalyst uses magnesium oxides as a carrier, uses iron oxides as main catalyzing components and uses molybdenum as an assistant catalyzing component to form a Fe/Mo/MgO three-phase metallic oxide catalyst; the molar ratio of the ferrum, the molybdenum and the magnesium in the catalyst is 0.5-5: 0.01-0.5: 10-30. The present invention has the following preparation method that ferrous metal salt, molybdic metal salt or molybdic oxides and magnesic metal salt are taken according to the molar ratio and uniformly mixed in deionized water or an alcohol solution; the solution is frozen under the temperature of from-100 to-40DEG. C; then, 12-48h primary drying processing is carried out to solid formed by being frozen under the temperature of from-40 to-10DEG. C; 6-12h secondary drying processing is carried out under the temperature of from 20 to 60 DEG C again. The present invention has the advantages of strong catalyst activity, high utilization rate, simple manufacturing process and uniform diameters of the single wall carbon nanotubes prepared with the catalyst.
Description
Technical field
The present invention relates to a kind of metal oxide catalyst for preparing SWNT and preparation method thereof.
Background technology
SWNT is seamless, the hollow tube that is curled into by hexagonal carbon atom looped network lattice, and each is reined in by half richness that face carbon ball forms end to end, similar graphite, the electronics that existence can move freely in the carbon valence link of CNT.Relative multiple-wall carbon nanotube, SWNT has the material behavior of many excellences.Among all preparation methods, chemical vapour deposition technique (CVD) is because its equipment, simple to operate, small investment, and characteristics such as reaction temperature is low are considered to the method for tool Commercial Prospect.Present SWNT is produced required Preparation of catalysts method and is emerged in an endless stream, but because its utilization rate and catalytic efficiency are not high, thereby the SWNT output that obtains is not high, and impurities is more in the primary product.
Summary of the invention
The purpose of this invention is to provide a kind of highly active metal oxide catalyst that is used for a large amount of manufacture order wall carbon nanotubes and preparation method thereof.
Metal oxide catalyst of the present invention is to be carrier with magnesia, the oxide that forms with iron is the main catalytic composition, with molybdenum is the Fe/Mo/MgO three-phase metal oxide catalyst that helps catalyst component to form, and iron in the catalyst: molybdenum: the mol ratio of magnesium is 0.5～5: 0.01～0.5: 10～30.Optimum mole ratio is for being 1～2: 0.01～0.2: 10～20.
In this metal oxide catalyst, select magnesium nitrate for use, magnesium acetate, magnesium chloride, magnesium sulfate, magnesium oxalate or magnesium ethylate are as the raw material that forms magnesium oxide carrier, select ferric nitrate for use, ferric acetate, iron chloride, ferric sulfate or ferric oxalate form the oxide of main catalytic composition iron, and molybdenum is selected from the oxide of molybdate or molybdenum.
The preparation process of metal oxide catalyst of the present invention is as follows: get the slaine of iron, slaine or the oxide of molybdenum and the slaine of magnesium of molybdenum in molar ratio, evenly be mixed in deionized water or the ethanolic solution, under-100～-40 ℃ that above-mentioned solution is freezing, carry out the primary drying processing of 12～48h then in-40～-10 ℃ of solids, under 20～60 ℃, carry out the redrying of 6～12h again and handle freezing formation.
Need not the preparation that calcination processing promptly can be used for SWNT through above-mentioned cryodesiccated catalyst.
Metal oxide catalyst of the present invention is used to prepare SWNT to carry out on fixed bed gas continuous-flow reacting furnace.A certain amount of catalyst is placed on places fixed bed gas continuous-flow reacting furnace on the quartz boat, feed methane and hydrogen or the nitrogen or the inert gas of certain flow, methane flow is 25～500sccm, be preferably 50～100sccm, hydrogen or nitrogen or inert gas flow are 50～400sccm, be preferably 200～400sccm, reaction temperature is controlled at 800～1200 ℃, be preferably 900～1000 ℃, reacted 10～60 minutes, the product of collection is the SWNT of metal oxide catalyst preparation of the present invention.
Metal oxide catalyst provided by the invention is active strong, and utilization rate is higher, with the SWNT diameter homogeneous of this Preparation of Catalyst, is 0.88 ± 0.1nm.And this catalyst preparation process process is simple and easy, and good reproducibility need not calcination processing.Synthetic SWNT output height, purity is higher, and degree of graphitization is very high.
Description of drawings
Fig. 1 is the SEM photo of the SWNT that makes with catalyst of the present invention;
Fig. 2 is the TEM photo of the SWNT that makes with catalyst of the present invention.
Fig. 3 is the TG curve of the SWNT that makes with catalyst of the present invention.
The specific embodiment
Embodiment 1
Get molybdenum oxide and join deionized water solution, added thermal agitation 0.5 hour, dissolve up to complete reaction at 80 ℃.Nine nitric hydrate iron, magnesium ethylate are dissolved in respectively in the above-mentioned solution that contains molybdenum, stirred 1 hour, evenly mix, iron in the solution: molybdenum: the mol ratio of magnesium is 2: 0.5: 15.Again with above-mentioned mixed solution in-60 ℃ freezing, the primary drying that carries out 36h in-30 ℃ of solids with freezing formation is handled then, to remove the crystallization water in the lyophilized solid, handles 30 ℃ of redryings of carrying out 6h again.Promptly can be used for the preparation of SWNT through above-mentioned cryodesiccated catalyst.
The preparation of SWNT is carried out on fixed bed gas continuous-flow reacting furnace.0.112 gram catalyst is put into flat-temperature zone, stove stage casing, and the feeding flow velocity is that methane and the flow of 70sccm is the hydrogen of 300sccm, and the control reaction temperature is 1000 ℃, reacts to make bunchy SWNT 0.165 gram after 30 minutes.The stereoscan photograph of product as shown in Figure 1, transmission electron microscope photo is as shown in Figure 2.
Embodiment 2
Get molybdenum acid ammonia and join deionized water solution, added thermal agitation 0.5 hour, dissolve up to complete reaction at 80 ℃.Nine nitric hydrate iron, magnesium ethylate are dissolved in respectively in the above-mentioned solution that contains molybdenum, stirred 1 hour, evenly mix, iron in the solution: molybdenum: the mol ratio of magnesium is 1: 0.1: 15, again with above-mentioned mixed solution in-40 ℃ freezing, the primary drying that carries out 24h in-30 ℃ of solids with freezing formation is handled then, to remove the crystallization water in the lyophilized solid, handle 40 ℃ of redryings of carrying out 6h again.Promptly can be used for the preparation of SWNT through above-mentioned cryodesiccated catalyst.
The preparation of carbon pipe is carried out on fixed bed gas continuous-flow reacting furnace.0.103 gram catalyst is put into flat-temperature zone, stove stage casing, and the feeding flow velocity is that methane and the flow velocity of 75sccm is the hydrogen of 200sccm, and the control reaction temperature is 1000 ℃, reacts to make SWNT 0.176 gram after 30 minutes.The TG curve of product as shown in Figure 3.
Claims (1)
1. preparation method who prepares the metal oxide catalyst of SWNT, it is characterized in that step is as follows: by iron: molybdenum: the mol ratio of magnesium is 0.5～5: 0.01～0.5: 10～30, get the slaine of iron, slaine or the oxide of molybdenum and the slaine of magnesium of molybdenum, evenly be mixed in deionized water or the ethanolic solution, under-100～-40 ℃ that above-mentioned solution is freezing, carry out the primary drying processing of 12～48h then in-40～-10 ℃ of solids, under 20～60 ℃, carry out the redrying of 6～12h again and handle freezing formation.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100499010A CN1318135C (en) | 2005-06-01 | 2005-06-01 | Catalyst of metallic oxide for preparing nanowall nano carbon pipe and preparation process thereof |
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| CNB2005100499010A CN1318135C (en) | 2005-06-01 | 2005-06-01 | Catalyst of metallic oxide for preparing nanowall nano carbon pipe and preparation process thereof |
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| CN1724345A CN1724345A (en) | 2006-01-25 |
| CN1318135C true CN1318135C (en) | 2007-05-30 |
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| CN113731433B (en) * | 2021-08-30 | 2024-02-02 | 福建海梵领航科技有限公司 | Trace molybdenum doped iron-based catalyst and preparation method and application thereof |
| CN115403029B (en) * | 2022-08-31 | 2024-01-30 | 聚源材料科技(遵义)有限公司 | Preparation method of single-walled carbon nanotube |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1476930A (en) * | 2003-07-08 | 2004-02-25 | 浙江大学 | Bimetal oxide catalyst and method using it to prepare single-wall nano carbon tube whose diameter can be controlled |
| CN1476929A (en) * | 2003-07-08 | 2004-02-25 | 浙江大学 | Denitration catalyst using CeTi2Ob as carrier and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1476930A (en) * | 2003-07-08 | 2004-02-25 | 浙江大学 | Bimetal oxide catalyst and method using it to prepare single-wall nano carbon tube whose diameter can be controlled |
| CN1476929A (en) * | 2003-07-08 | 2004-02-25 | 浙江大学 | Denitration catalyst using CeTi2Ob as carrier and its preparation method |
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