CN108262486B - A method of filling non-precious metal and/or metal carbide nanoparticles in small diameter carbon nanotubes - Google Patents
A method of filling non-precious metal and/or metal carbide nanoparticles in small diameter carbon nanotubes Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 75
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- 238000011049 filling Methods 0.000 title claims abstract description 45
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- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 3
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 claims description 3
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- WQAVHVQYKSYTII-UHFFFAOYSA-N carbon monoxide;cyclohepta-1,3,5-triene;molybdenum Chemical compound [Mo].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1C=CC=CC=C1 WQAVHVQYKSYTII-UHFFFAOYSA-N 0.000 claims description 2
- XAOCYVWRKJTXOL-UHFFFAOYSA-N carbon monoxide;cyclooctatetraene;iron Chemical group [Fe].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=CC=C1 XAOCYVWRKJTXOL-UHFFFAOYSA-N 0.000 claims description 2
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- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 4
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 2
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- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- 241000065385 Ophiomyia simplex Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- DEIHRWXJCZMTHF-UHFFFAOYSA-N [Mn].[CH]1C=CC=C1 Chemical compound [Mn].[CH]1C=CC=C1 DEIHRWXJCZMTHF-UHFFFAOYSA-N 0.000 description 1
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- CHVJITGCYZJHLR-UHFFFAOYSA-N cyclohepta-1,3,5-triene Chemical compound C1C=CC=CC=C1 CHVJITGCYZJHLR-UHFFFAOYSA-N 0.000 description 1
- KDUIUFJBNGTBMD-VXMYFEMYSA-N cyclooctatetraene Chemical compound C1=C\C=C/C=C\C=C1 KDUIUFJBNGTBMD-VXMYFEMYSA-N 0.000 description 1
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- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
本发明公开了一种在小管径碳纳米管管腔内填充非贵金属和/或非贵金属碳化物纳米粒子的方法，小管径碳纳米管指内径小于3nm的碳纳米管，包括单壁和双壁碳纳米管。具体地说，该方法涉及利用易挥发、易氧化的金属有机复合物，在惰性气氛中经一定温度的气化以后，通入到抽真空的碳纳米管管腔内，并利用控制氧化的方法将其固载在碳纳米管管腔内，再经高温还原或退火分别得到金属或金属碳化物纳米粒子。本方法具有简单、易于操作和控制的特点。
The invention discloses a method for filling non-noble metal and/or non-noble metal carbide nanoparticles in the lumen of a small-diameter carbon nanotube. The small-diameter carbon nanotube refers to a carbon nanotube with an inner diameter of less than 3 nm, including single-wall and Double-walled carbon nanotubes. Specifically, the method involves the use of volatile and oxidizable metal-organic compounds, which are gasified at a certain temperature in an inert atmosphere, and then passed into the vacuumed carbon nanotube lumen, and the method of controlling oxidation It is immobilized in the cavity of the carbon nanotube, and then subjected to high-temperature reduction or annealing to obtain metal or metal carbide nanoparticles respectively. The method is simple, easy to operate and control.
Description
Technical Field
The invention relates to a method for loading non-noble metal nano particles in a small-caliber carbon nanotube cavity, in particular to a method for selectively and uniformly dispersing non-noble metal particles in the small-caliber carbon nanotube cavity with the caliber of 0.8-3 nm.
Background
The carbon nanotube is a carbon material which is formed by winding single-layer or multi-layer graphene along a chiral vector and has a quasi-one-dimensional nano-scale tubular cavity structure. Since the discovery, carbon nanotubes have been receiving much attention from researchers in various fields due to unique physical and chemical properties on a nanometer scale. One of the most interesting properties of carbon nanotubes is that their quasi-one-dimensional nanoscale tubular structures can be used as nano-scale containers or reactors, and a series of novel nanocomposites with specific structures and properties can be obtained by encapsulating exogenous substances therein [ Monthioux et al J.Mater. Res.2006,21,2774 ]. Recent studies have shown that metals or metal carbides encapsulated in the carbon nanotube lumens have superior electronic, optical and mechanical properties compared to materials supported outside the tubes or in bulk phase, and thus have potential application prospects in various fields, including catalysis [ x.l.pan, x.h.bao, Accounts of Chemical Research,2011,44, 553-; S.A. miners, A.N.Khlobystov, Chemical Society reviews,2016,45, 4727-; sithorarnan, L.J.Wilson, International Journal of Nanomedicine,2006,1, 291-295.). In particular, metals with magnetic properties, such as iron, cobalt, nickel, have enhanced coercivity and excellent oxidation resistance after being wrapped in the lumen of a Carbon nanotube, thereby having long-term stability, and have wider applications in various fields, such as magnetic thermal therapy [ a.taylor, s.m.p.wirth, Carbon,2010,48, 2327-.
A series of relatively mature and effective methods have been established in recent years for filling various nanomaterials into the lumen of multi-walled carbon tubes (tube inner diameter >4 nm). The earliest report was that in 1993, Ajayan et al filled PbO in MWNT by a fusion method [ P.M.Ajayan and S.lijima, Nature,1993,361,333-334 ]. Thereafter, various filling methods are reported in succession [ J.Sloan, R.Tenne, Journal of Materials Chemistry,1997,7, 1089-. Compared with a multi-wall tube, the small-caliber carbon nanotube, especially the single-wall carbon nanotube has more uniform pipe diameter distribution, larger aspect ratio and fewer defects, and often has stronger confinement effect on object substances, so that a composite material with more excellent performance is expected to be obtained. Therefore, the filling of the carbon nanotubes with small tube diameter is more concerned by researchers. The filling methods established at present mainly include solution phase filling, supercritical filling, melt method filling and gas phase filling. The single-walled tube filling was first reported to be a method using a solution phase, in which ruthenium trichloride was filled into a tube cavity and metallic ruthenium was obtained by further hydrogen reduction [ J.Sloan, M.L.H.Green, Chemical communications,1998,3,347-348 ]. However, the filling rate obtained by this method is generally not more than 30% because solvent molecules cannot enter the inner part of the tube cavity in the filling process. Supercritical filling is a special solution phase filling method, mainly involving the introduction of a guest substance into a tube cavity by means of a supercritical fluid, and is generally less used because it involves operating conditions of high temperature and high pressure. The filling by the fusion method is to seal the object substance and the carbon tubes in a quartz device after vacuum pumping, melt the object substance by heating, and fill the object substance into the tube cavity in a liquid phase by using capillary action, and the filling rate of the method is generally lower than 60%, and the filler is required to have high thermal stability and low surface tension, so the application range is limited [ J.P.Cleuziou, M.Monthioux, Acs Nano,2011,5, 2348-. The gas phase method is the most effective way to fill the carbon nanotubes with small tube diameter, and the capillary condensation mechanism is involved. High efficiency filling of noble metals in small-diameter carbon tubes with filling rates above 85% has been achieved currently using gas phase processes, such as rhenium [ h.b.zhang, x.l.pan, x.h.bao, Chemical Science,2013,4, 1075-. However, the efficient filling of non-noble metals such as iron, cobalt, nickel and molybdenum in the carbon tube with small tube diameter has not been reported. Chinese patent application publication No. CN102806108A (application No. 201110144034.4) discloses a method of filling ferrocene in carbon tubes having an inner diameter of 1 to 20nm using a vapor phase method and obtaining metallic iron by further heat treatment, but since ferrocene has high thermal stability and volatility, most of iron particles are deposited on the outer wall of the tube during thermal decomposition, resulting in a low filling rate. The patent also discloses that molybdenum pentachloride is used as a precursor to fill the carbon tube, but the vapor pressure of the molybdenum pentachloride is low, so that the filling rate of a vapor phase method is not high, and the precursor contains a large amount of chlorine element, so that the chlorine element is difficult to completely remove in the post-treatment process and has great influence on the subsequent application of the chlorine element. Pichler reports vapor phase filling of single-walled carbon tubes with nickel acetylacetonate as a precursor and obtaining metallic nickel by vacuum heat treatment, but also a large number of nickel particles are deposited outside the tubes during vacuum heat treatment [ h.shiozawa, t.pichler, Sci Rep,2015,5 ]. For the filling of cobalt in a small-diameter carbon tube, only a liquid phase method is currently reported, and the filling rate is low [ c.z.Loebick, L.d.Pfefferle, J.Phys.chem.C,2010,114, 11092-11097; J. -P.Cleuziou, M.Monthioux, Acs Nano,2011,5, 2348-. The method is characterized in that non-noble metals such as iron, cobalt, nickel and molybdenum and carbide nanostructures thereof are efficiently filled in a thin-wall carbon nanotube with a tube cavity smaller than 3nm, and further property and application research on the non-noble metals is not realized until now and is a bottleneck.
Disclosure of Invention
The invention solves the problems: the method for filling non-noble metal and/or metal carbide nano particles in the carbon nano tube with small tube diameter overcomes the defects of the prior art, utilizes a volatile and easily-oxidized non-noble metal organic compound as a precursor to directionally and uniformly disperse the non-noble metal and the carbide nano particles thereof in the tube cavity of the carbon nano tube with the tube cavity diameter less than 3nm, and has the characteristics of simplicity and easiness in operation and control.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for filling non-noble metal and/or metal carbide nano particles in the carbon nano tube with small tube diameter is suitable for all the carbon nano tubes with hollow hole channels, especially for the carbon nano tubes with small tube diameter distributed between 0.8-3nm, including single-wall and double-wall carbon nano tubes.
The method comprises the following specific steps:
(1) pretreatment of the carbon nanotubes: dispersing original carbon nanotubes in a mixed solution of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic treatment for 4-7h, filtering, leaching to neutrality, performing vacuum freeze sublimation drying for 50-100h, and treating in hydrogen or argon at the temperature of 1000 ℃ for 3-5h by using 700-;
(2) packaging the spare carbon tube in a container, evacuating the container to dewater to a vacuum degree of 10-2Gasifying a metal precursor below Pa, introducing the gasified metal precursor into the carbon tube, and maintaining the gasified metal precursor at the temperature of more than 70 ℃ for more than 24 hours to obtain a metal precursor carbon nanotube compound;
(3) controlling oxidative decomposition of the obtained metal precursor carbon nanotube composite in an oxidizing atmosphere, soaking the metal precursor carbon nanotube composite in dilute nitric acid or hydrochloric acid solution, washing the metal precursor carbon nanotube composite with water to be neutral, and drying the metal precursor carbon nanotube composite to obtain a metal oxide carbon nanotube composite;
(4) and (3) carrying out heat treatment on the metal oxide carbon nanotube composite obtained in the step (3) at the temperature of 800 ℃ for 1-5h in hydrogen or inert atmosphere to obtain non-noble metal and/or non-noble metal carbide nano particles encapsulated in the tube cavity of the small-diameter carbon tube.
The non-noble metals comprise iron, cobalt, nickel and molybdenum, and the listed non-noble metals have important application prospects in the fields of catalysis, nanoelectronics, nanomedicine and the like, and are obtained by the applicant through repeated experiments and comparisons.
The small-caliber carbon nano tube is a single-wall carbon nano tube or a double-wall carbon nano tube with the inner diameter of only 0.8-3 nm.
The carbon nano tube obtained by mixed acid ultrasonic treatment is a high-purity carbon nano tube carrier with the purity of more than 95 percent and the length of about 0.4 to 1.0 mu m.
In the mixed solution of concentrated sulfuric acid and concentrated nitric acid, the volume ratio of mixed acid is 1: 10, preferably 1: 3, the mixed acid in the proportion range has strong oxidizability, and can effectively purify and truncate the carbon nano tube.
The metal precursor refers to one or more than two of metal-organic compounds which have melting points lower than 175 ℃ and are easy to oxidize; the metal precursors refer to cyclooctatetraene tricarbonyl iron, cyclohexadiene tricarbonyl iron, cycloheptatriene tricarbonyl molybdenum, tricarbonyl cyclopentadienyl manganese, cobaltocene or nickelocene, and all the selected metal precursors have the advantages of easy volatilization, small molecular weight, small toxicity and the like.
In the step (2), in the filling process of the carbon nano tube, the mass ratio of the metal precursor to the carbon nano tube is 0.1-10 so as to realize the high dispersion of the metal and the carbide thereof in the tube cavity of the carbon nano tube.
In the step (2), the metal precursor is gasified and introduced into the carbon tube, and after the carbon tube is maintained at 70-120 ℃ for 24-72 hours, the oxidative decomposition in the step (3) is carried out, so that the metal precursor can completely permeate the carbon nanotube.
The oxidative decomposition conditions in the step (3) are as follows: the pressure is 0.1-8Mpa, the temperature is 25-300 ℃, the temperature is maintained for 1-24h in the atmosphere with the oxygen content of 1-100 percent, and the oxidative decomposition condition is mild and the efficiency is high.
The concentration of nitric acid or hydrochloric acid used in the step (3) is 0.1-2M, the drying temperature is 60-120 ℃, and the treatment condition can effectively remove residual metal precursor species outside the tube.
In the step (4), the inert atmosphere is one of nitrogen, argon or helium.
The electron microscope test result shows that the metal oxide obtained by the controlled oxidation treatment is highly dispersed in the tube cavity of the carbon tube, and the metal or metal carbide nano particles with the particle size distribution of about 1-3nm can be obtained by further high-temperature reduction or annealing treatment.
Compared with the prior art, the invention has the advantages that:
(1) the invention utilizes the gaseous state form of the volatile and easily oxidized non-noble metal organic compound precursor for filling, and adopts the oxidation control mode to avoid the phenomenon that the metal precursor migrates to the outside of the tube in the thermal decomposition process, thereby realizing the selective filling of non-noble metal nano particles in the open carbon nano tube cavity with the tube diameter of 0.8-3nm, including single-wall and double-wall carbon nano tubes.
(2) The invention has mild conditions in the filling process, simple equipment requirements, simple and easy process operation, no damage to the tube wall of the carbon nano tube, and macroscopic magnitude (gram magnitude) applied to catalytic research can be obtained in a single experiment.
(3) The invention has high efficiency, and the filling rate of the obtained non-noble metal or carbide nano particles thereof in the carbon tube is up to more than 85 percent, which lays a material foundation for further researching the performance of the novel nano composite material.
Drawings
FIGS. 1 and 2 are electron micrographs of single-walled carbon nanotubes without nanoparticle modification after purification treatment for low and high resolution;
fig. 3 and 4 are high-angle annular dark field images and spherical aberration corrected high-angle annular dark field images of the metallic iron-filled single-walled carbon nanotubes prepared in example 2;
FIGS. 5 and 6 are high resolution electron micrographs of metallic cobalt-filled double-walled carbon nanotubes prepared in example 5;
fig. 7 and 8 are high-resolution electron micrographs of metallic molybdenum and molybdenum carbide filled double-walled carbon nanotubes prepared in example 4.
Detailed Description
To further illustrate the present invention, the following specific examples are set forth, but the scope of the claims of the present invention is not limited by these examples. Meanwhile, the embodiment only gives some conditions for achieving the purpose, but does not mean that the conditions must be met for achieving the purpose.
Example 1
Putting 4 parts of 60mg of original single-walled carbon nanotubes (SWCNTs) (with the inner diameter of 0.8-3nm) into four 100-milliliter round-bottom flasks, respectively adding 60mL of mixed acid (concentrated sulfuric acid: concentrated nitric acid: 3:1), simultaneously putting into an ultrasonic water bath, carrying out ultrasonic treatment for 5.5 hours, maintaining the temperature of the water bath at 40-50 ℃, taking 45mL of supernatant after ultrasonic treatment, rinsing to be neutral, and carrying out vacuum freeze drying for 90 hours. And (3) treating the dried sample in argon at 1000 ℃ for 4h, wherein the flow of the argon is 50mL/min, cooling to room temperature, and taking out for later use.
Fig. 1 and 2 are electron micrographs of low resolution and high resolution of purified truncated carbon nanotubes without nanoparticle modification. The electron microscope photo shows that the length of the truncated and purified single-wall carbon nano-tube is uniformly distributed in the range of 0.4-1.0 μm, the tube cavity is hollow, and the purity is higher than 95%.
Example 2
1g of the purified single-walled carbon nanotubes (s-SWCNTs) obtained in example 1 was weighed into a vacuum filling apparatus, and 100mg of cyclooctatetraene tricarbonyl was placed into the other end of the vacuum apparatus. At 1X 10-4Device program for placing carbon nano tube under Pa vacuum conditionThe temperature is increased to 450 ℃, the heating rate is 5 ℃/min, and the temperature is kept at 450 ℃ for 16 hours. And (3) after cooling, mixing the carbon nano tube and the precursor in vacuum, and treating for 72 hours in an oven at 80 ℃ to obtain the iron precursor-carbon tube compound. And (3) after the compound is exposed to the atmosphere, placing the compound in an autoclave, filling high-purity oxygen of 8Mpa, carrying out oxidation treatment at 100 ℃ for 24h, cooling to room temperature, taking out, putting into 2M nitric acid solution, stirring and washing for 1h, carrying out suction filtration, leaching to be neutral, drying at 100 ℃ for 12h, taking out, and carrying out hydrogen reduction treatment at 450 ℃ for 5h to obtain a sample filled with metallic iron in 1g of single-walled carbon nanotubes.
Fig. 3 and 4 are high-angle annular dark field images and spherical aberration-corrected high-angle annular dark field images of the metallic iron-filled carbon nanotubes prepared in the present example. The electron microscope photo shows that the iron nano particles are efficiently filled in the single-walled carbon nano tube with the tube diameter of 0.8-3.0nm, and the filling rate is as high as more than 85%.
Example 3
500mg of the purified single-walled carbon nanotubes (s-SWCNTs) obtained in example 1 were weighed into a vacuum filling apparatus, and 50. mu.L of tricarbonyl cyclohexadiene iron was placed into the other end of the vacuum apparatus. At 1X 10-4And (3) programming the device with the carbon nano tube to 450 ℃ under the Pa vacuum condition, wherein the heating rate is 5 ℃/min, and the temperature is kept at 450 ℃ for 16 hours. And (3) after cooling, mixing the carbon nano tube and the precursor in vacuum, and treating for 72 hours in a 50 ℃ oven to obtain the iron precursor-carbon tube compound. And (3) after the compound is exposed to the atmosphere, placing the compound in a high-pressure kettle, filling high-purity oxygen of 8Mpa, carrying out oxidation treatment at 100 ℃ for 24h, cooling to room temperature, taking out, putting into 2M nitric acid solution, stirring and washing for 1h, carrying out suction filtration, leaching to neutrality, drying at 100 ℃ for 12h, taking out, and carrying out hydrogen reduction treatment at 450 ℃ for 5h to obtain a sample filled with metallic iron in the single-walled carbon nanotube.
Example 4
500mg of purified double-wall carbon nanotubes (s-DWCNTs) are weighed into a vacuum filling device, and 50mg of molybdenum tricarbonyl cycloheptatriene is placed at the other end of the vacuum device. At 1X 10-4And (3) programming the device with the carbon nano tube to 450 ℃ under the Pa vacuum condition, wherein the heating rate is 5 ℃/min, and the temperature is kept at 450 ℃ for 16 hours. Cooling, mixing the carbon nanotube and the precursor in vacuum, and oven-treating at 100 deg.C for 48 deg.Ch, obtaining the molybdenum precursor-carbon tube compound. And after the compound is exposed to the atmosphere, placing the compound in the air, carrying out oxidation treatment at normal pressure and room temperature for 24 hours, carrying out hydrogen reduction treatment at 550 ℃ for 5 hours to obtain a sample filled with the metal molybdenum in the 500mg double-walled carbon nanotube, and carrying out annealing treatment in argon at 800 ℃ for 3 hours to obtain a sample filled with the molybdenum carbide in the 500mg double-walled carbon nanotube.
Fig. 7 and 8 are high-resolution electron micrographs of metallic molybdenum and molybdenum carbide-filled carbon nanotubes prepared in this example. The electron microscope photo shows that metal molybdenum and molybdenum carbide nano particles are respectively and efficiently filled in the tube cavity of the double-wall carbon nano tube with the tube diameter of about 1.7nm, and the filling rate is up to 90 percent.
Example 5
500mg of purified double-wall carbon nano tubes (s-DWCNTs) are weighed and placed in a vacuum filling device, and 50mg of cobaltocene is placed at the other end of the vacuum device. At 1X 10-4And (3) programming the device with the carbon nano tube to 450 ℃ under the Pa vacuum condition, wherein the heating rate is 5 ℃/min, and the temperature is kept at 450 ℃ for 16 hours. And after cooling, mixing the carbon nano tube and the precursor in vacuum, and treating for 48 hours in an oven at 110 ℃ to obtain the cobalt precursor-carbon tube composite. And after the compound is exposed to the atmosphere, placing the compound in a high-pressure kettle, filling air of 1.0Mpa, carrying out oxidation treatment at room temperature for 6h, putting the compound into a 2M nitric acid solution, stirring and washing for 1h, carrying out suction filtration, leaching to be neutral, drying at 100 ℃ for 12h, taking out the compound, and carrying out hydrogen reduction treatment at 350 ℃ for 5h to obtain a sample with metal cobalt filled in a 500mg double-walled carbon nanotube.
Fig. 5 and 6 are high-resolution electron micrographs of the metallic cobalt-filled carbon nanotubes prepared in this example. The electron microscope photo shows that the cobalt nano particles are efficiently filled in the double-walled carbon nano tube with the tube diameter of 0.8-3.0nm, and the filling rate is as high as more than 85%.
Example 6
1g of the purified single-walled carbon nanotubes (s-SWCNTs) obtained in example 1 was weighed into a vacuum filling device, and 100mg of nickelocene was placed into the other end of the vacuum device. At 1X 10-4And (3) programming the device with the carbon nano tube to 450 ℃ under the Pa vacuum condition, wherein the heating rate is 5 ℃/min, and the temperature is kept at 450 ℃ for 16 hours. After cooling down, the carbon nano tube and the precursor are mixed under vacuumAnd (3) performing oven treatment at 110 ℃ for 48h to obtain the nickel precursor-carbon tube composite. And (3) after the compound is exposed to the atmosphere, placing the compound in an autoclave, filling air of 0.5Mpa, carrying out oxidation treatment at room temperature for 6h, putting the compound into a 2M nitric acid solution, stirring and washing for 1h, carrying out suction filtration, leaching to be neutral, drying at 100 ℃ for 12h, taking out the compound, and carrying out hydrogen reduction treatment at 500 ℃ for 5h to obtain a sample filled with metallic nickel in 1g of single-walled carbon nanotubes.
The above examples are provided only for the purpose of describing the present invention, and are not intended to limit the scope of the present invention. The scope of the invention is defined by the appended claims. Various equivalent substitutions and modifications can be made without departing from the spirit and principles of the invention, and are intended to be within the scope of the invention.
Claims (11)
1. A method for filling non-noble metal in a carbon nanotube with small tube diameter is characterized by comprising the following steps:
(1) pretreatment of the carbon nanotubes: dispersing original carbon nano tubes in a mixed solution of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic treatment, filtering, leaching to neutrality, performing vacuum freeze sublimation drying, and treating at the temperature of 700-;
(2) packaging the spare carbon tube in a container, heating the container, evacuating and dehydrating to reach a vacuum degree of 10-2The precursor of non-noble metal is gasified and introduced into the carbon tube after the temperature is reduced below Pa, and is maintained for more than 24 hours at the temperature of more than 70 ℃ to obtain the carbon nanotube composite of the precursor of non-noble metal;
(3) controlling the oxidative decomposition of the obtained non-noble metal precursor carbon nanotube compound under an oxidizing atmosphere, wherein the oxidative decomposition conditions are as follows: maintaining the pressure at 0.1-8Mpa and temperature at 25-300 deg.C in the atmosphere with oxygen content of 1-100% for 1-24h, adding into dilute solution of nitric acid or hydrochloric acid, stirring, washing, vacuum filtering, washing with water to neutrality, and drying to obtain non-noble metal oxide carbon nanotube composite;
(4) carrying out heat treatment on the non-noble metal oxide carbon nanotube compound obtained in the step (3) for 1-5h at the temperature of 800 ℃ in the hydrogen atmosphere to obtain non-noble metal nano particles encapsulated in the tube cavity of the small-diameter carbon tube;
the small-caliber carbon nano tube is a single-wall carbon nano tube or a double-wall carbon nano tube with the inner diameter of only 0.8-3 nm.
2. A method for filling non-noble metal carbide nano particles in a carbon nano tube with a small tube diameter is characterized by comprising the following steps:
(1) pretreatment of the carbon nanotubes: dispersing original carbon nano tubes in a mixed solution of concentrated sulfuric acid and concentrated nitric acid, performing ultrasonic treatment, filtering, leaching to neutrality, performing vacuum freeze sublimation drying, and treating at the temperature of 700-;
(2) packaging the spare carbon tube in a container, heating the container, evacuating and dehydrating to reach a vacuum degree of 10-2The precursor of non-noble metal is gasified and introduced into the carbon tube after the temperature is reduced below Pa, and is maintained for more than 24 hours at the temperature of more than 70 ℃ to obtain the carbon nanotube composite of the precursor of non-noble metal;
(3) controlling the oxidative decomposition of the obtained non-noble metal precursor carbon nanotube compound under an oxidizing atmosphere, wherein the oxidative decomposition conditions are as follows: maintaining the pressure at 0.1-8Mpa and temperature at 25-300 deg.C in the atmosphere with oxygen content of 1-100% for 1-24h, adding into dilute solution of nitric acid or hydrochloric acid, stirring, washing, vacuum filtering, washing with water to neutrality, and drying to obtain non-noble metal oxide carbon nanotube composite;
(4) carrying out heat treatment on the non-noble metal oxide carbon nanotube compound obtained in the step (3) for 1-5h at the temperature of 300-800 ℃ in a hydrogen atmosphere, and then carrying out heat treatment for 1-5h at the temperature of 300-800 ℃ in an inert atmosphere to obtain non-noble metal carbide nanoparticles encapsulated in the tube cavity of the small-diameter carbon tube;
the small-caliber carbon nano tube is a single-wall carbon nano tube or a double-wall carbon nano tube with the inner diameter of only 0.8-3 nm.
3. The method according to claim 1 or 2, characterized in that: the non-noble metal comprises one of iron, cobalt, nickel and molybdenum.
4. The method according to claim 1 or 2, characterized in that: the carbon nano tube obtained by mixed acid ultrasonic treatment is a carbon nano tube carrier with the purity of more than 95 percent and the length of 0.4 to 1.0 mu m.
5. The method according to claim 1 or 2, characterized in that: in the mixed solution of the concentrated sulfuric acid and the concentrated nitric acid, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 10.
6. the method of claim 5, wherein: in the mixed solution of the concentrated sulfuric acid and the concentrated nitric acid, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 3.
7. the method according to claim 1 or 2, characterized in that: the non-noble metal precursor refers to one or more than two of metal organic compounds with melting points lower than 175 ℃ and easy oxidation; the non-noble metal precursor is cyclooctatetraene tricarbonyl iron, cyclohexadiene tricarbonyl iron, cycloheptatriene tricarbonyl molybdenum, cobaltocene or nickelocene.
8. The method according to claim 1 or 2, characterized in that: in the step (2), in the filling process of the carbon nano tube, the mass ratio of the non-noble metal precursor to the carbon tube is 0.1-10.
9. The method according to claim 1 or 2, characterized in that: in the step (2), the non-noble metal precursor is gasified and introduced into the carbon tube, and after the carbon tube is maintained at the temperature of 70-120 ℃ for 24-72 hours, the oxidative decomposition in the step (3) is carried out.
10. The method according to claim 1 or 2, characterized in that: the concentration of nitric acid or hydrochloric acid used in the step (3) is 0.1-2M, and the drying treatment temperature is 60-120 ℃ after water washing.
11. The method of claim 2, wherein: in the step (4), the inert atmosphere is one of nitrogen, argon or helium.
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