CN103170633B - Preparation method of pod-shaped carbon nanotube encapsulation non-noble metal nano-particles - Google Patents
Preparation method of pod-shaped carbon nanotube encapsulation non-noble metal nano-particles Download PDFInfo
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- CN103170633B CN103170633B CN201110435881.6A CN201110435881A CN103170633B CN 103170633 B CN103170633 B CN 103170633B CN 201110435881 A CN201110435881 A CN 201110435881A CN 103170633 B CN103170633 B CN 103170633B
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Abstract
The invention discloses a preparation method of pod-shaped carbon nanotube encapsulation non-noble metal nano-particles. Particularly, the preparation method is based on a solvothermal method, and the non-noble metal nano-particles are generated through the direct reaction of alkali metal or derivatives and second metallocene compounds at low temperature. The prepared carbon nanotube is in a neat pod-shaped structure, and the metal nano-particles are in an elementary substance state. The preparation method of the pod-shaped carbon nanotube encapsulation non-noble metal nano-particles has the advantages of being simple and easy to operate and control.
Description
Technical field
The present invention relates to a kind of preparation method of pod-like carbon nanotube encapsulation base metal simple substance nano particle.
Background technology
Metal nanoparticle because of its peculiar physicochemical characteristics as dimensional effect, quantum effect etc. have caused the extensive concern of researcher, it is all widely used (" nanometer technology preparation method " (U.S.) Edward L. Wolf Xue Dongfeng translates, China Machine Press 2010 years) in fields such as physics, chemistry, biologies.
The preparation method that metal current nano particle is conventional comprises (" preparation method of nano material and application thereof " Sun Yuxiu, Zhang Dawei, the big China Textiles Press of Jin Zheng 2010) such as sublimation recrystallization method, ion sputtering process, mechanical milling method, chemical precipitation method, x ray irradiation x synthetic methods, but these methods have a common shortcoming to be exactly the nano particle especially non-noble metal nanoparticles extremely unstable in an atmosphere of preparation, easily oxidized and reunite.Be difficult at present to prepare the good elemental of dispersion and can at the non-noble metal nanoparticles of stable existence under atmospheric environment.
Therefore, we have developed a kind of synthetic method of non-noble metal nanoparticles of pod-like carbon nanotube encapsulation elemental.This pod-like CNT has regular carbonization structure, thus effectively prevent non-noble metal nanoparticles and contact with the direct of air.Due to prepared metal nanoparticle by the CNT of pod-like and external environment completely isolated, so this material can the mal-condition such as acid and alkali resistance well, high temperature, high light.Therefore, this material is expected to be used as the catalyst of the catalytic reaction under or harsh environmental conditions severe at some, as the catalyst in the eelctro-catalyst of acidic fuel cell or traditional heterogeneous catalytic system.In addition, because the metal nanoparticle of encapsulation can electronic structure (the H.Shiozawa et al. of modulation CNT tube wall, Phys.Rev.B 77,153402 (2008) .), therefore, this material is also expected to there is potential application in fields such as electronic device, superconduction, biology sensors.
Summary of the invention
The invention discloses a kind of preparation method of pod-like carbon nanotube encapsulation base metal simple substance nano particle.
Specifically, the method is a kind of method based on solvent heat, utilizes alkali metal or derivatives thereof and metallocene compound directly to react generation at low temperatures.Prepared CNT has regular pod-like structures, and packaged metal nanoparticle is elemental.
A kind of preparation method of pod-like carbon nanotube encapsulation non-noble metal nanoparticles:
(1) by alkali metal or derivatives thereof and metallocene compound at inert gas shielding lower seal in autoclave;
(2) autoclave in (1) is kept 1-20 hour in 150-500 DEG C;
(3) sample of (2) gained is processed 3-8 hour in acid solution; Then wash respectively with water and ethanol and filter, until solution is in neutral;
(4) by (3) gained sample drying, the base metal simple substance nano particle of pod-like carbon nanotube encapsulation is namely obtained.
Described alkali metal or derivatives thereof is one or more in lithium, sodium, potassium, lithium nitride, sodium azide;
Described metallocene compound can be one or two or more kinds in ferrocene, cobaltocene or dicyclopentadienyl nickel; Base metal is one or two or more kinds in iron, cobalt or nickel;
The mass ratio of described alkali metal or derivatives thereof and metallocene compound is 1: 4-6: 1;
Described inert gas is nitrogen, argon gas or helium.
Described acid solution can be sulfuric acid solution (5-80wt.%), hydrochloric acid solution (10-30wt.%) or salpeter solution (10-50wt.%).。
Reaction temperature is generally 200-450 DEG C, preferably 250-400 DEG C, is preferably 250-300 DEG C; Keep temperature to be generally 2-15 hour, preferably 3-12 hour, is preferably 6-8 hour.
Baking temperature is 60-120 DEG C, and drying time is 6-12 hour.
The present invention is a kind of method based on solvent heat, utilizes alkali metal or derivatives thereof and metallocene compound directly to react generation at low temperatures.Prepared CNT has regular pod-like structures, and packaged metal nanoparticle is elemental.This method has simply, the feature be easy to operate and control.
Tool of the present invention has the following advantages:
1. presoma metallocene compound can be metallocene compound can be in ferrocene, cobaltocene or dicyclopentadienyl nickel, and its wide material sources are cheap.
2. adopt the method for a step thermal response, method is simple.Reaction temperature is relatively low, and condition easily controls, and is easy to operation.
3. can realize preparation in macroscopic quantity, be easy to amplify and produce.
Accompanying drawing explanation
Fig. 1 is the transmission electricity (TEM) of embodiment 1 sample; TEM shows that gained sample has obvious pod-like structures, and the spacing of lattice of packaged nano particle is
, [110] crystal face of corresponding fe.
Fig. 2 is the X-ray diffraction spectrum (XRD) of embodiment 1 sample; XRD shows that the sample of gained has three diffraction maximums, respectively (002) crystal face of corresponding graphitic carbon, (110) and (200) crystal face of fe.
Fig. 3 is the x-ray photoelectron power spectrum (XPS) of embodiment 1 sample: (a) composes entirely; (b) Fe 2p simple spectrum.The bright gained sample of full stave is only containing C, O, Fe tri-kinds of elements, and Fe 2p simple spectrum shows that Fe element is the fe of zero-valent state.
Detailed description of the invention
Below by embodiment, whole process is described in further detail, but right of the present invention is not by the restriction of these embodiments.Meanwhile, embodiment just gives the partial condition realizing this object, but and does not mean that must meet these conditions just can reach this object.
Embodiment 1
1. 3.0g sodium azide and 3.0g ferrocene are sealed in 40mL autoclave under nitrogen protection.
2. the autoclave in (1) is kept 4 hours in 350 DEG C.
3. by the sample of (2) gained in 18% (mass concentration) hydrochloric acid solution process 5 hours.Then wash repeatedly with water and ethanol and filter respectively.
4. namely (3) gained sample is obtained beanpod ferrum nano material in 12 hours in 120 DEG C of dryings.
Primary first-order equation can obtain pure beanpod ferrum nano material 1.4 grams.Transmission electron microscope (see Fig. 1), X-ray diffraction spectrum (see Fig. 2) and x-ray photoelectron power spectrum (see Fig. 3) show that gained sample has pod-like structures, and packaged iron nano-particle is elemental.
Embodiment 2
1. 1.0g lithium nitride and 3.0g ferrocene are sealed in 40mL autoclave under nitrogen protection.
2. the autoclave in (1) is kept 6 hours in 450 DEG C.
3. with the step 3 of embodiment 1.
4. with the step 4 of embodiment 1.
Primary first-order equation can obtain pure beanpod ferrum nano material 1.1 grams.Analytical test (transmission electron microscope, X-ray diffraction spectrum and x-ray photoelectron power spectrum) shows that gained sample has pod-like structures, and packaged iron nano-particle is elemental.
Embodiment 3
1. by 2.0g sodium and 3.5g cobaltocene at argon shield lower seal in 40mL autoclave.
2. the autoclave in (1) is kept 10 hours in 250 DEG C.
3. with the step 3 of embodiment 1.
4. with the step 4 of embodiment 1.
Primary first-order equation can obtain pure beanpod ferrum nano material 1.6 grams.Analytical test (transmission electron microscope, X-ray diffraction spectrum and x-ray photoelectron power spectrum) shows that gained sample has pod-like structures, and packaged cobalt nano-particle is elemental.
Embodiment 4
1. by 4.0g potassium and 2.0g dicyclopentadienyl nickel at argon shield lower seal in 40mL autoclave.
2. the autoclave in (1) is kept 3 hours in 500 DEG C.
3. with the step 3 of embodiment 1.
4. with the step 4 of embodiment 1.
Primary first-order equation can obtain pure beanpod ferrum nano material 0.8 gram.Analytical test (transmission electron microscope, X-ray diffraction spectrum and x-ray photoelectron power spectrum) shows that gained sample has pod-like structures, and packaged nano nickel particles is elemental.
Application examples
1. adopt embodiment 1 to obtain beanpod ferrum nano material 150.0mg and carry out preparation of low carbon olefines by synthetic gas reaction as catalyst.
2. reaction condition: pressure 0.5MPa, temperature 320 DEG C, pulp furnish CO: H
2=1: 1 (V/V), air speed 3500h
-1.
The conversion ratio of 3.CO is 8.6%, and selectivity of light olefin is 52.3%, reacts 200 hours its performances and has no inactivation.
This pod-like CNT has regular carbonization structure, thus effectively prevent non-noble metal nanoparticles and contact with the direct of air.Due to prepared metal nanoparticle by the CNT of pod-like and external environment completely isolated, so this material can the mal-condition such as acid and alkali resistance well, high temperature, high light.Therefore, this material is expected to be used as the catalyst of the catalytic reaction under or harsh environmental conditions severe at some, as the catalyst in the eelctro-catalyst of acidic fuel cell or traditional heterogeneous catalytic system.
Claims (8)
1. a preparation method for pod-like carbon nanotube encapsulation non-noble metal nanoparticles, is characterized in that:
(1) by alkali metal or derivatives thereof and metallocene compound at inert gas shielding lower seal in autoclave;
(2) autoclave in (1) is kept 1-20 hour in 150-500 DEG C;
(3) sample of (2) gained is processed 3-8 hour in acid solution; Then wash respectively with water and ethanol and filter, until solution is in neutral;
(4) by (3) gained sample drying, the non-noble metal nanoparticles of pod-like carbon nanotube encapsulation is namely obtained.
2., according to the method described in claim 1, it is characterized in that:
Described alkali metal or derivatives thereof is one or more in lithium, sodium, potassium, lithium nitride, sodium azide;
Described metallocene compound is one or two or more kinds in ferrocene, cobaltocene or dicyclopentadienyl nickel, and base metal is one or two or more kinds in iron, cobalt or nickel;
The mass ratio of alkali metal or derivatives thereof and metallocene compound is 1:4-6:1.
3. method according to claim 1, is characterized in that:
Step (1) inert gas is nitrogen, argon gas or helium.
4. method according to claim 1, is characterized in that: the sulfuric acid solution of step (3) acid solution to be mass concentration be 5-80wt.%, mass concentration to be the hydrochloric acid solution of 10-30wt.% or mass concentration be in 10-50wt.% salpeter solution one or two or more kinds.
5. method according to claim 1, is characterized in that:
Step (2) reaction temperature is 200-450 DEG C, and maintenance temperature is 2-15 hour.
6. method according to claim 1, is characterized in that:
Step (2) reaction temperature is 250-400 DEG C, and maintenance temperature is 3-12 hour.
7. method according to claim 1, is characterized in that:
Step (2) reaction temperature is 250-300 DEG C; Maintenance temperature is 6-8 hour.
8. method according to claim 1, is characterized in that:
Step (4) baking temperature is 60-120 DEG C, and drying time is 6-12 hour.
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| CN104841924B (en) * | 2014-02-19 | 2017-11-21 | 中国科学院大连化学物理研究所 | A kind of preparation method of the fully enclosed metal nanoparticle of carbon |
| CN108968148A (en) * | 2018-06-08 | 2018-12-11 | 滁州卷烟材料厂 | A kind of composite filter tip addition material reducing determination of hydrogen cyanide in mainstream cigarette smoke |
| CN114149526B (en) * | 2021-12-09 | 2023-04-18 | 宁波大学 | Pod-shaped nanotube and preparation method and application thereof |
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