CN104944410A - Method for synthesis of cobalt nanoparticle and bamboo-like nitrogen doped carbon nanotube composite material - Google Patents
Method for synthesis of cobalt nanoparticle and bamboo-like nitrogen doped carbon nanotube composite material Download PDFInfo
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Abstract
The invention discloses a method for synthesis of a cobalt nanoparticle and bamboo-like nitrogen doped carbon nanotube composite material. The method includes: dissolving a soluble cobalt salt and an amine polymer in a hydrophilic reagent according to a mole ratio of 1:(2-200), performing evaporation at 60DEG C, conducting grinding after cooling, performing calcination at 400-1400DEG C under nitrogen atmosphere, then treating the sample with acid, and carrying out washing, centrifugation and drying so as to obtain the cobalt nanoparticle and bamboo-like nitrogen doped carbon nanotube composite material. The obtained cobalt nanoparticles have small particle size and are employed to coat the head of a carbon nanotube evenly so as to combine tightly with the carbon nanotube. The composite material has application prospects in fuel cell anode materials, lithium ion battery cathode materials and the like. The method designed by the invention has the advantages of easily available raw materials, simple process and no pollution, short preparation period, mild reaction conditions, low cost, and mass synthesis capability, etc.
Description
Technical field
The present invention relates to a kind of method of synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material, belong to carbon nanotube one-dimensional composite material preparing technical field.
Background technology
The appearance of carbon nanotube opens the new important research field of nano material science and technology, low-dimension nano material scientific research band to one dimension (1D) epoch, 1991, electron microscope expert Iijima (Iijima) doctor of Japanese NEC Corporation basic research laboratories surprisingly found carbon nanotube (Carbon nanotube).As typical 1D nano structural material, carbon nanotube shows novel physics-chem characteristic, especially high thermostability and surface carrier mobility, make carbon nanotube at new forms of energy, sensor, ultracapacitor, being also used widely in the fields such as field emission tube, is just successfully applied to conductive structure material, sensing and display equipment, new forms of energy store and the field such as conversion system in short several years.The huge investigation and application value that carbon nanotube shows also result in investigator and adulterates and compound to carbon nanotube.Various heteroatomic doping is had at present for carbon nanotube, such as boron, nitrogen, phosphorus, sulphur etc. adulterate to electronics or electrophilic heteroatoms, change the out-shell electron number of the surface carbon atom of carbon nanotube, electronegativity and atomic size, due to the structure of special electronegativity and uniqueness, these doped carbon nanometer pipe materials show special characteristic electron and surface imperfection, there is excellent mechanics, electricity and catalytic performance, opto-electronic device can be widely used in, biochemical sensor, catalyzer, ultracapacitor, lithium ion battery, the field such as fuel cell and solar cell, especially in the electrochemical reaction field highly depending on bill of material interface performance, doped carbon nanometer pipe shows superior performance especially.But the performance and application of these a series of innovations of carbon nanotube but depends on the controlled mass-producing preparation of material.The special performance of carbon nano-tube material depends on its length and diameter, thus carrys out by the regulation and control of nanoscale and appearance structure the Some Questions To Be Researched that design and synthesis carbon nanotube is considered to modern chemistry and Materials science.Transition metal and nitrogen doped corrugated carbon nanotube matrix material cause the interest of many scientific workers, due to structure and the excellent performance of its uniqueness, make it in matrix material, electronics, sensor, lithium ion battery, ultracapacitor, fuel cell etc., have important potential application.But at present for nitrogen doped corrugated carbon nanotube material, it is simple and easy, not good way in cheap and a large amount of synthesis.And current synthetic method synthesis bamboo-like carbon nano tubes, caliber is usually extremely uneven, and impurity is more, cost is higher, is difficult to continuous batch and produces.And carbon nanotube and transition metal compound normally load is at carbon nanotube outer, and transition metal is easy to be oxidized to oxide compound, due to the electroconductibility that it is bad, thus affects the electrochemical performance of carbon nanotube.
Preparing the method that carbon nano tube compound material extensively adopts at present is graphite arc discharge method, chemical vapour deposition (CVD) and hydrothermal method etc.Although graphite arc discharge method can be prepared on a large scale, and output is comparatively large, and impurity is more, needs comparatively loaded down with trivial details subsequent disposal.And although chemical vapour deposition can prepare high-quality carbon nanotube, its output is lower, and highly depends on growing substrate, and cost is higher, is not suitable for industrial applications.Comparatively speaking, thermal decomposition method is fairly simple synthetic method efficiently, and building-up process is simply controlled, and raw material is cheap and easy to get, is applicable to industrialized developing application.
It is simple that the present invention has synthetic method, and obtained carbon nanotube diameter is even, and productive rate is higher, and cobalt nanometer particle compound is comparatively tight, is applicable to extensive preparation.According to the knowledge of the applicant, have no the method reporting synthesis cobalt nanometer particle and bamboo-like carbon nano tubes matrix material up to now simultaneously.
Summary of the invention
The object of the invention is to solve prior art complex steps, and gained carbon nanotube diameter is uneven, compound is tight, cannot mass-produced problem, provides a kind of cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite process.
The object of the invention is to be achieved through the following technical solutions.
The present invention proposes a kind of cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite process, and concrete steps are as follows:
Step one, by cobalt salt and amine polymer according to mol ratio 1:(2 ~ 200) be dissolved in respectively in methyl alcohol, heating evaporation under 60 degree, carry out grinding after naturally cooling to room temperature after evaporate to dryness and obtain sample powder;
Step 2, sample powder step one obtained are put into tube furnace and are passed into nitrogen and calcine,
Step 3, the sample products acid treatment sample that step 2 is obtained, then use deionized water and absolute ethanol washing centrifugal after, just obtain Bamboo-shaped nitrogen-doped carbon nanometer pipe after putting into vacuum drying oven drying.
Described cobalt salt raw material is: Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous acetate, cobalt chloride, one or more the mixing salt in rose vitriol;
Described amine polymer is: trimeric cyanamide, dicyan diamino, urea, one or more the mixture in cyanamide;
Described acid is: hydrochloric acid, sulfuric acid, nitric acid, one or more mixing solutions of acetic acid.
Beneficial effect
1, a kind of method of synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material of the present invention, its morphology is characterized as Bamboo-shaped nanotube, uniform diameter, cobalt nanometer particle is wrapped in carbon nanotube head, can be used for preparing fuel cell, electrode of super capacitor active material and catalyzer etc.
2, a kind of method of synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material of the present invention, simple to operate, with low cost, can prepare on a large scale, whole reaction process does not need specific apparatus, temperature of reaction is between 400 ~ 1400 DEG C, and Product size and pattern are even, cobalt nanometer particle and bamboo-like carbon nano tubes compound tight.
3, a kind of method of synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material of the present invention, adopt thermal decomposition method to have simple advantage, reaction time is short, and reaction yield is high, and composite effect is good.And cobalt nanometer particle carries out catalysis to carbon nanotube wherein, therefore obtained product structure is peculiar, and degree of graphitization is high, without other impurity.Prepare carbon nano tube compound material with the method such as the chemical vapour deposition generally adopted and hydro-thermal, the method designed by the present invention has the advantages such as product is even, compound tight, a large amount of synthesis, is applicable to suitability for industrialized production and mass-producing is applied.
Accompanying drawing explanation
Fig. 1 is for illustrating the X-ray diffracting spectrum of the carbon nano tube compound material material prepared by case study on implementation;
Fig. 2 is for illustrating the scanning electron microscope diagram of the carbon nano tube compound material material prepared by case study on implementation;
Fig. 3 is for illustrating the low power transmission electron microscope figure of the carbon nano tube compound material material prepared by case study on implementation;
Fig. 4 is for illustrating the high power transmission electron microscope figure of the carbon nano tube compound material material prepared by case study on implementation;
Fig. 5 is for illustrating the high-resolution-ration transmission electric-lens figure of the carbon nano tube compound material material prepared by case study on implementation;
Fig. 6 is for illustrating the X-ray photoelectron spectroscopic analysis of the carbon nano tube compound material material prepared by case study on implementation;
Fig. 7 is for illustrating the Raman energy spectrum figure of the carbon nano tube compound material material prepared by case study on implementation;
Embodiment
Embodiment 1
(1) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and trimeric cyanamide are dissolved in methyl alcohol respectively according to mol ratio 1:200, magnetic agitation 30 minutes, to fully dissolving, then heating evaporation under 60 degree, carries out grinding and obtain sample powder after evaporate to dryness after naturally cooling to room temperature.
(2) obtained sample powder is put into tube furnace to pass into nitrogen and calcine, is warming up to 400 degree with 5 degree of per minutes and keeps 1 hour, then rise to 700 degree with 10 degree of per minutes and keep 3 hours, obtain sample products.
(3) the HCl treatment sample of the sample products 0.5M obtained, then use deionized water and absolute ethanol washing centrifugal after, just obtain cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material after putting into vacuum drying oven 80 degree of dryings.
Embodiment 2
(1) cobaltous acetate and Dicyanodiamide are dissolved in ethanol respectively according to mol ratio 1:2, magnetic agitation 30 minutes, to fully dissolving.Then heating evaporation under 60 degree, carries out grinding and obtain sample powder after evaporate to dryness after naturally cooling to room temperature.
(2) obtained sample powder is put into tube furnace to pass into nitrogen and calcine, is warming up to 400 degree with 5 degree of per minutes and keeps 1 hour, then rise to 700 degree with 10 degree of per minutes and keep 3 hours, obtain sample products.
(3) the vitriolization sample of the sample products 0.5M obtained, then use deionized water and absolute ethanol washing centrifugal after, just obtain cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material after putting into vacuum drying oven 80 degree of dryings.
Embodiment 3
(1) cobalt chloride and cyanamide are dissolved in deionized water respectively according to mol ratio 1:10, magnetic agitation 30 minutes, to fully dissolving.Then heating evaporation under 60 degree, carries out grinding and obtain sample powder after evaporate to dryness after naturally cooling to room temperature.
(2) obtained sample powder is put into tube furnace to pass into nitrogen and calcine, is warming up to 500 degree with 2 degree of per minutes and keeps obtaining sample products in 3 hours.
(3) the nitric acid treatment sample of the sample products 0.5M obtained, then use deionized water and absolute ethanol washing centrifugal after, just obtain cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material after putting into vacuum drying oven 80 degree of dryings.
Embodiment 4
(1) rose vitriol and trimeric cyanamide are dissolved in ethylene glycol respectively according to mol ratio 1:20, magnetic agitation 30 minutes, to fully dissolving.Then heating evaporation under 60 degree, carries out grinding and obtain sample powder after evaporate to dryness after naturally cooling to room temperature.
(2) obtained sample powder is put into tube furnace to pass into nitrogen and calcine, is warming up to 400 degree with 5 degree of per minutes and keeps 3 hours, then rise to 1400 degree with 10 degree of per minutes and keep 2 hours, obtain sample products.
(3) the acetic acid treatment sample of the sample products 0.5M obtained, then use deionized water and absolute ethanol washing centrifugal after, just obtain cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material after putting into vacuum drying oven 80 degree of dryings.
Embodiment 5
(1) cobaltous acetate and Dicyanodiamide are dissolved in the mixed solvent of ethanol and methyl alcohol according to mol ratio 1:50 respectively, magnetic agitation 30 minutes, to fully dissolving.Then heating evaporation under 60 degree, carries out grinding and obtain sample powder after evaporate to dryness after naturally cooling to room temperature.
(2) obtained sample powder is put into tube furnace to pass into nitrogen and calcine, is warming up to 400 degree with 5 degree of per minutes and keeps 3 hours, then rise to 1400 degree with 10 degree of per minutes and keep 2 hours, obtain sample products.
(3) the vitriolization sample of the sample products 0.5M obtained, then use deionized water and absolute ethanol washing centrifugal after, just obtain cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material after putting into vacuum drying oven 80 degree of dryings.
Embodiment 6
(1) mixture of cobalt chloride and Dicyanodiamide and trimeric cyanamide is dissolved in the mixed solvent of methyl alcohol respectively according to mol ratio 1:50, magnetic agitation 30 minutes, to fully dissolving.Then heating evaporation under 60 degree, carries out grinding and obtain sample powder after evaporate to dryness after naturally cooling to room temperature.
(2) obtained sample powder is put into tube furnace to pass into nitrogen and calcine, is warming up to 300 degree with 3 degree of per minutes and keeps 3 hours, then rise to 900 degree with 5 degree of per minutes and keep 2 hours, obtain sample products.
(3) the HCl treatment sample of the sample products 0.5M obtained, then use deionized water and absolute ethanol washing centrifugal after, just obtain cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material after putting into vacuum drying oven 80 degree of dryings.
Embodiment 7
(1) mixture of cobalt chloride and cobaltous acetate and trimeric cyanamide are dissolved in the mixed solvent of ethanol respectively according to mol ratio 1:100, magnetic agitation 30 minutes, to fully dissolving.Then heating evaporation under 60 degree, carries out grinding and obtain sample powder after evaporate to dryness after naturally cooling to room temperature.
(2) obtained sample powder is put into tube furnace to pass into nitrogen and calcine, is warming up to 1000 degree with 5 degree of per minutes and keeps 3 hours, obtain sample products.
(3) the acetic acid treatment sample of the sample products 0.5M obtained, then use deionized water and absolute ethanol washing centrifugal after, just obtain cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material after putting into vacuum drying oven 80 degree of dryings.
Embodiment 8
(1) mixture of rose vitriol and cobaltous acetate and Dicyanodiamide trimeric cyanamide are dissolved in the mixed solvent of ethanol respectively according to mol ratio 1:20, magnetic agitation 30 minutes, to fully dissolving.Then heating evaporation under 60 degree, carries out grinding and obtain sample powder after evaporate to dryness after naturally cooling to room temperature.
(2) obtained sample powder is put into tube furnace to pass into nitrogen and calcine, is warming up to 400 degree with 2 degree of per minutes and keeps 3 hours, then be warming up to 900 degree with 3 degree of per minutes and obtain sample products.
(3) hydrochloric acid of the sample products 0.5M obtained and sulfuric acid mixture processing sample, then use deionized water and absolute ethanol washing centrifugal after, just obtain cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material after putting into vacuum drying oven 80 degree of dryings.
Fig. 1 is the X ray diffracting spectrum of carbon nano tube compound material, and obtained material is cobalt nanometer particle and bamboo-like carbon nano tubes matrix material, and material crystalline is good.Fig. 2 is the scanning electron microscope diagram sheet of carbon nano tube compound material, and evenly, cobalt nanometer particle is wrapped in head for obtained material diameter and pattern.Fig. 3 is the low power transmission electron micrograph of carbon nano tube compound material, and obtained material is Bamboo-shaped nano tube structure, and its length is about 1 ~ 3um, and diameter is about 80 ~ 100nm.Fig. 4 is the high power transmission electron micrograph of carbon nano tube compound material, obtained material is Bamboo-shaped nano tube structure, its uniform diameter, the obvious Fig. 5 of bamboo joint structure is the high resolution transmission electron microscopy picture of carbon nano tube compound material, obtained material is typical Bamboo-shaped multi-wall carbon nano-tube tubular construction, and compound is tight, can be observed (111) face of cobalt nanometer particle by lattice fringe, prove that cobalt nanometer particle is wrapped in head, its diameter is about 80nm.Fig. 6 is the X-ray photoelectron spectroscopic analysis of carbon nano tube compound material, due to obtained cobalt nanometer particle and nitrogen doped corrugated shape matrix material, only C detected, N, O, and Co element, occur without other impurity elements, illustrate that prepared carbon nanotube is by N doping, and better with Co Nanocomposites, without other impurity.Fig. 7 is the Raman energy spectrum figure of carbon nano tube compound material, and at 1329D band and 1573G with obvious characteristic peak, be the characteristic peak of carbon nano-tube material, the degree of graphitization indicating matrix material is high, and conductivity well, has good chemical property.
Claims (6)
1. a method for pyrolyzing synthesis cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material, is characterized in that: concrete steps are as follows:
Step one, cobalt salt and amine polymer to be dissolved in hydrophilic solvent respectively, blending ratio is the mol ratio of cobalt salt and amine polymer is 1:(2 ~ 200), heating evaporation under 60 degree, carries out grinding and obtain sample powder after evaporate to dryness after naturally cooling to room temperature;
Step 2, sample powder step one obtained are put into tube furnace and are passed into nitrogen and calcine;
Step 3, the sample products acid treatment sample that step 2 is obtained, then use deionized water and absolute ethanol washing centrifugal after, just obtain Bamboo-shaped nitrogen-doped carbon nanometer pipe after putting into vacuum drying oven drying.
2. the method for a kind of pyrolyzing synthesis cobalt nanometer particle as claimed in claim 1 and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material, it is characterized in that: described hydrophilic solvent is: methyl alcohol, ethanol, deionized water, ethylene glycol, in one or more mixed solvent.
3. the method for a kind of pyrolyzing synthesis cobalt nanometer particle as claimed in claim 1 and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material, it is characterized in that: described cobalt salt raw material is: Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous acetate, cobalt chloride, rose vitriol, in one or more mixing salt.
4. as the method for a kind of pyrolyzing synthesis cobalt nanometer particle as claimed in claim 1 and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material, it is characterized in that: described amine polymer is: trimeric cyanamide, dicyan diamino, urea, one or more the mixture in cyanamide.
5. the method for a kind of pyrolyzing synthesis cobalt nanometer particle as claimed in claim 1 and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material, is characterized in that: institute's calcining temperature any number of degrees from 400 ~ 1200 degree of intervals in nitrogen.
6. the method for a kind of pyrolyzing synthesis cobalt nanometer particle as claimed in claim 1 and Bamboo-shaped nitrogen-doped carbon nanometer pipe matrix material, is characterized in that: described acid is: hydrochloric acid, sulfuric acid, nitric acid, one or more mixing solutions of acetic acid.
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