CN100577329C - Method for preparing nano metallic nano granular coating with carbon - Google Patents
Method for preparing nano metallic nano granular coating with carbon Download PDFInfo
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- CN100577329C CN100577329C CN200710168612A CN200710168612A CN100577329C CN 100577329 C CN100577329 C CN 100577329C CN 200710168612 A CN200710168612 A CN 200710168612A CN 200710168612 A CN200710168612 A CN 200710168612A CN 100577329 C CN100577329 C CN 100577329C
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Abstract
The invention relates to a method for preparing Carbon-encapsulated magnetic metal nano particles, which is characterized in that: dissolving the annular structure hydrocarbon and the soluble metal salt respectively in the solvent, forming the two solution, then mixing the two solution uniformly to get the mixed liquor; evaporating the mixed liquor to dryness to get the solid mixture of the metal salt and the hydrocarbon; grinding the solid mixture into powder; treating the powder by heat treatment in inert atmosphere such as nitrogen; dipping the power in concentrated nitric acid or treat the powder by reflow process, then diluting the nitric acid solution with water; separating the solid by centrifugal force or filtering, and then gathering the solid; washing the solid with distilled water until the lotion is litmusless, then separating the solid by centrifugal force or filtering again; drying the solid, then getting the composite material of Carbon-encapsulated magnetic metal nano particles. The invention has the advantages of proper condition, low cost and simple technology.
Description
Technical field
The present invention relates to a kind of method for preparing nano metallic nickel granular material coating with carbon.
Background technology
Nano metallic nickel granular material coating with carbon (hereinafter to be referred as CEMNs) is meant that the nano particle with magnetic metals such as iron, cobalt, nickel is a core, and the outside coats concentric layered shell polysaccharide graphite-structure layer and a kind of composite with Nano capsule structure of forming.The carbonaceous of outside not only can protect nano metallic nickel granular material to prevent its quick oxidation, can also effectively stop the reunion between the nano particle.Therefore, CEMNs has broad application prospects, as the high density magnetic recording material, and magnetic seal fluid, magnetic ink and biomedical sector mri contrast agent, target medicine carrier etc.
According to existing document, the CEMNs preparation method mainly comprises: arc discharge method, improve arc discharge method, ion beam sputtering, chemical vapour deposition technique, wet chemistry method, with the Nano diamond is the solid reaction process of carbon source, and with metal impregnation method such as high temperature graphitization then in the how empty carbon.Arc discharge method is as negative electrode with carbon-point; metal, alloy or carbon embedding metal carry out arc discharge as anode under different protective atmospheres, collect discharging product; just obtained containing the mix products of more CEMNs behind cleaning, purifying, this is the most traditional preparation method of CEMNs.Improved arc discharge method has adopted the alternating current discharge, and by the tenor in the change electrode, and discharging condition can obtain the CEMNs of higher yields.Ion beam sputtering be with metal and high purity graphite as target, thereby sputter simultaneously forms the method for CEMNs film.Chemical vapour deposition (CVD) is to be precursor with the magnetic metal organic matter, and weak reducing gas as carrier gas reduction reaction takes place at high temperature, thereby forms CEMNs.Is precursor as people such as Z.H.Wang with carbonyl cobalt [Co (CO)], and CO is carrier gas, has synthesized the carbon covered metal cobalt nanometer particle at 480 ℃.Wet chemistry method is to form CEMNs in solution or molten mass, as Kentaroh Kosugi etc. at FeCl
3Add ultra-fine CaC in the acetonitrile solution
2Synthesized the FeC that is isolated from each other
2Nano particle has obtained CEMNs 250 ℃ of reducing atmosphere roastings.2003, Japanese Satoshi Tomita etc. was blended in 1700 ℃ of annealing with magnetic metallic powder and diamond nano powder, has obtained the CEMNs sample, the only several nanometers of sample China and Mexico layer integument thickness.
But above-mentioned all these method synthesis conditions are relatively harsher, all need complicated instrument and equipment or expensive raw material, the cost height, and productive rate is low.Wherein some method also can form other carbon structure product and carbide when forming CEMNs, can not guarantee purity.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing nano metallic nickel granular material coating with carbon, this method preparation condition gentleness, with low cost, technology is simple.
To achieve these goals, technical scheme of the present invention is: a kind of method for preparing nano metallic nickel granular material coating with carbon, it comprises the steps:
1) soluble metallic salt is dissolved in the solvent, is mixed with the soluble metal salting liquid of 0.5～3mol/L; To have the circulus hydrocarbon is dissolved in and is mixed with the carbon source solution that mass concentration is 30-60% in the solvent; According to having the circulus hydrocarbon: the ratio of the metal equivalent=1kg in the soluble metallic salt: 0.05～0.5mol, the soluble metal salting liquid is joined in the carbon source solution, under 60～90 ℃ of water bath condition, stirred 0.5～5 hour; Make soluble metal salting liquid and the abundant mixing of carbon source solution on the one hand; Evaporate most of volume on the other hand and make mixture be condensed into glue, under 110～130 ℃ of temperature, the solvent evaporate to dryness is obtained the solid mixture of carbon source-slaine then;
Described soluble metallic salt is any one or any mixing more than two kinds in ferrous metal salt, cobalt slaine, the nickel slaine, is any proportioning during any mixing more than two kinds;
2) with the solid mixture ball milling or the grind into powder of step 1);
3) with step 2) powder in inert atmosphere in 600～1000 ℃ of heat treatments 4～8 hours, keep reducing atmosphere to cool to room temperature with the furnace, powdery product;
4) the cooled powdery product of step 3) was soaked 8-24 hour in the red fuming nitric acid (RFNA) of 6～14mol/L or reflow treatment 4-10 hour, dilute with water salpeter solution to 0.1～0.5mol/L, centrifugation or filter out solid, collect solid matter, solid matter is washed with distilled water to washing lotion and is neutral, centrifugation or filter out solid again, drying can obtain nano metallic nickel granular material coating with carbon (CEMNs).
Institute of the present invention weighing-appliance circulus hydrocarbon means the hydrocarbon that has polynary carbocyclic ring in its structure, and this compound solubility in water or ethanol or oxolane equal solvent is bigger.Tool circulus hydrocarbon comprises sucrose, glucose, maltose, PVP, naphthalene or anthracene etc.
The alleged soluble metallic salt of the present invention means the inorganic salts of iron, cobalt, nickel, and can dissolve in water or ethanol or oxolane equal solvent.As nitrate, chloride or anhydrous chloride etc.
The present invention will have circulus hydrocarbon (abbreviation carbon source) and soluble metallic salt and be dissolved in respectively and form solution in the solvent, two kinds of solution evenly be mixed obtaining mixed liquor then; The mixed liquor evaporate to dryness is obtained the solid mixture of slaine and hydrocarbon; With the solid mixture grind into powder; Powder is heat-treated under inert atmospheres such as nitrogen, in red fuming nitric acid (RFNA), soak or reflow treatment, the dilute with water salpeter solution, centrifugation or filter out solid, collect solid matter, solid matter is washed with distilled water to washing lotion and is neutral, centrifugation or filter out solid again, and drying can obtain the nano metallic nickel granular material coating with carbon composite.
The present invention has the following advantages:
1, with soluble metallic salt (soluble inorganic salt) as source metal, tool circulus hydrocarbons such as table sugar are carbon source, the raw material cheapness, are easy to get, and are with low cost.
2, source metal and carbon source are mixed in solution and the colloid substance of evaporating solvent formation at a lower temperature, can reach the mixing of molecular level.
3, milled processed such as ball milling makes the grain refine of slaine and carbon source mixture, is easy to make the CEMNs of particle high degree of dispersion.
4, reaction condition gentleness, technology is simple, and the reaction process controllability is strong.
5, preparation technology's integral production cost is low.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the nano metallic nickel granular material coating with carbon of embodiment 1 preparation.
Fig. 2 is the X ray diffracting spectrum of the nano metallic nickel granular material coating with carbon of embodiment 2 preparations.
Fig. 3 is the transmission electron micrograph of the nano metallic nickel granular material coating with carbon of embodiment 2 preparations.
Fig. 4 is the X ray diffracting spectrum of the nano metallic nickel granular material coating with carbon of embodiment 3 preparations.
The specific embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
With 25mL concentration be the iron nitrate solution of 1mol/L to join the 50mL mass concentration be in 40% the aqueous sucrose solution, be transferred to after 2 hours in 130 ℃ the baking oven dry 2 hours 80 ℃ stirred in water bath; Collect dried solid matter, with planetary ball mill with ball milling under the rotating speed of 580rpm 2 hours (with Al
2O
3Be abrasive media).The powder that obtains behind the ball milling is placed the quartz boat of tubular heater, and heat treatment is 6 hours under 900 ℃ of condition of nitrogen gas, naturally cools to room temperature under the blanket of nitrogen.Take out sample, after refluxing 12 hours in the red fuming nitric acid (RFNA) of 14mol/L, the dilute with water salpeter solution filters to 0.2mol/L, collects solid portion, is washed with distilled water to washing lotion again and is neutral, can obtain nano metallic nickel granular material coating with carbon after the drying.X-ray diffraction (XRD) analysis result shows that the grain size of the metallic iron nano particle that is coated is 15nm (Fig. 1).
Embodiment 2:
With 25mL concentration be the cobalt nitrate solution of 1mol/L to join the 50mL mass concentration be in 40% the polyvinyl pyrrolidone aqueous solution, be transferred to after 2 hours in 130 ℃ the baking oven dry 2 hours 90 ℃ stirred in water bath; Collect dried solid matter, with planetary ball mill with ball milling under the rotating speed of 580rpm 2 hours (is abrasive media with the agate).The powder that obtains behind the ball milling is placed the quartz boat of tubular heater, and heat treatment naturally cooled to room temperature in the same atmosphere after 8 hours under 800 ℃ the condition of nitrogen gas.Take out sample, in the red fuming nitric acid (RFNA) of 14mol/L, soak after 12 hours sonic oscillation 30 minutes, the dilute with water salpeter solution is to 0.3mol/L, and solid matter is collected in centrifugation, be washed with distilled water to washing lotion and be neutral, can obtain nano metallic nickel granular material coating with carbon after the separation drying.X-ray diffraction analysis shows that sample forms (Fig. 2) by graphite and metallic cobalt.Transmission electron microscope (TEM) observation shows that the metallic cobalt nano particle diameter that is coated is 10～30nm, and the graphite shell thickness is 5～20 graphite-structure layers (Fig. 3).
Embodiment 3:
With 15mL concentration is that the iron nitrate solution of 1mol/L and nickel nitrate solution that 5mL concentration is 1mol/L mix, and joins the 50mL mass concentration and is in 40% the grape aqueous solution, is transferred to after 5 hours in 130 ℃ the baking oven dry 2 hours 70 ℃ stirred in water bath; Collect dried solid matter, with planetary ball mill 2 hours (Al of rotating speed ball milling with 580rpm
2O
3Be ball-milling medium).The powder that obtains behind the ball milling is placed the quartz boat of tubular heater, and annealing naturally cooled to room temperature after 8 hours under 900 ℃ the condition of nitrogen gas.Take out sample, after in the red fuming nitric acid (RFNA) of 14mol/L, refluxing 12 hours, dilute with water salpeter solution to 0.1～0.5mol/L, filter, the solid matter of collecting is washed repeatedly with distilled water, be neutral to washing lotion, filter out solid, promptly obtain nano metallic nickel granular material coating with carbon after the drying.X-ray diffraction (XRD) observed result shows that the grain size of the metallic iron nano particle that is coated is 15nm (Fig. 4).
Embodiment 4:
With 25mL concentration is that the tetrahydrofuran solution of the waterless cobaltous chloride of 1mol/L joins in the toluene solution that the 40mL mass concentration is 60% naphthalene, 90 ℃ stirred in water bath after 1.5 hours, in ventilating kitchen with dry 4 hours of infrared lamp irradiation; Collect dried solid matter, in mechanical mortar, grind and obtained mixed powder in 5 hours.Mixed powder is placed the quartz boat of tubular heater, and annealing naturally cooled to room temperature after 8 hours under 700 ℃ the argon gas condition.Take out sample, after in the red fuming nitric acid (RFNA) of 14mol/L, refluxing 12 hours, the dilute with water salpeter solution is to 0.1mol/L, filter out solid, collect solid matter, solid matter is washed with distilled water to washing lotion and is neutral, after leaching solid, solid matter collection, drying can be obtained nano metallic nickel granular material coating with carbon.Transmission electron microscope (TEM) observed result shows that the metallic cobalt nano particle diameter that is coated is 10～30nm, and the graphite shell thickness is 5～20 graphite-structure layers.
Embodiment 5:
With 25mL concentration is that the ferric chloride solution of 1mol/L joins in the ethanolic solution that the 50mL mass concentration is 40% vinyl pyrrolidone, 80 ℃ stirred in water bath after 2 hours, in ventilating kitchen with dry 2 hours of infrared lamp irradiation; Collect dried solid matter, with planetary ball mill ball milling 2 hours under the rotating speed of 580rpm.The powder that obtains behind the ball milling is placed the quartz boat of tubular heater, and annealing naturally cooled to room temperature after 8 hours under 600 ℃ the condition of nitrogen gas.Take out sample, after refluxing 12 hours in the red fuming nitric acid (RFNA) of 14mol/L, the dilute with water salpeter solution is to 0.5mol/L, filter, collect solid matter and be washed with distilled water to washing lotion and be neutral, centrifugation goes out solid, will solid matter collects, promptly obtains the carbon-clad metal iron nano-particle after the drying.X-ray diffraction (XRD) observed result shows that the grain size of the metallic iron nano particle that is coated is 12nm.
The concentration upper lower limit value of soluble metal salting liquid of the present invention, carbon source solution, and the upper lower limit value of the proportioning of soluble metal salting liquid and carbon source solution can both be realized the present invention; And cited soluble metallic salt, concrete material with circulus hydrocarbon can both be realized the present invention; And cited temperature, the upper lower limit value of time, can both realize the present invention; Do not enumerate embodiment one by one at this.
Claims (2)
1. a method for preparing nano metallic nickel granular material coating with carbon is characterized in that it comprises the steps:
1) soluble metallic salt is dissolved in the solvent, is mixed with the soluble metal salting liquid of 0.5～3mol/L; To have the circulus hydrocarbon is dissolved in and is mixed with the carbon source solution that mass concentration is 30-60% in the solvent; According to having the circulus hydrocarbon: the ratio of the metal equivalent=1kg in the soluble metallic salt: 0.05～0.5mol, the soluble metal salting liquid is joined in the carbon source solution, under 60～90 ℃ of water bath condition, stirred 0.5～5 hour; Under 110～130 ℃ of temperature, the solvent evaporate to dryness is obtained the solid mixture of carbon source-slaine then;
Described soluble metallic salt is any one or any mixing more than two kinds in ferrous metal salt, cobalt slaine, the nickel slaine, is any proportioning during any mixing more than two kinds;
2) with the solid mixture ball milling or the grind into powder of step 1);
3) with step 2) powder in inert atmosphere in 600～1000 ℃ of heat treatments 4～8 hours, keep reducing atmosphere to cool to room temperature with the furnace, powdery product;
4) the cooled powdery product of step 3) was soaked 8-24 hour in the red fuming nitric acid (RFNA) of 6～14mol/L or reflow treatment 4-10 hour, dilute with water salpeter solution to 0.1～0.5mol/L, centrifugation or filter out solid, collect solid matter, solid matter is washed with distilled water to washing lotion and is neutral, centrifugation or filter out solid again, drying can obtain nano metallic nickel granular material coating with carbon.
2. a kind of method for preparing nano metallic nickel granular material coating with carbon according to claim 1 is characterized in that: described tool circulus hydrocarbon is sucrose, glucose, maltose, PVP, naphthalene or anthracene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102500295A (en) * | 2011-10-26 | 2012-06-20 | 天津大学 | Preparation method of carbon-coated metallic nano-particles |
| CN102709017B (en) * | 2012-06-11 | 2015-07-01 | 合肥工业大学 | Preparation method of carbon-aerogel-based spherical anticorrosion magnetic material |
| CN102784913A (en) * | 2012-07-26 | 2012-11-21 | 天津大学 | Hydrothermal preparation method of carbon-coated iron nanoparticles |
| CN104493190B (en) * | 2014-12-17 | 2017-02-01 | 北京科技大学 | Production method of graphite/iron carbide/ iron nanocomposite |
| CN106825553B (en) * | 2017-02-07 | 2019-01-11 | 合肥工业大学 | A kind of preparation method of cobalt-nitrogen-carbon nucleocapsid hybrid hollow porous carbon ball |
| CN106908502B (en) * | 2017-03-27 | 2019-03-01 | 电子科技大学 | The preparation method of the glucose sensor enzyme electrode of carbon-coated magnetic ferrite modification |
| CN111515409B (en) * | 2020-04-08 | 2022-09-06 | 大连理工大学 | Preparation method of carbon-coated magnetic nickel-cobalt core-shell structure microspheres |
| CN114619025B (en) * | 2020-12-11 | 2023-09-29 | 国家能源投资集团有限责任公司 | Carbon-coated metal nanoparticle, and preparation method and application thereof |
| CN114291811A (en) * | 2021-12-29 | 2022-04-08 | 山西大学 | Simple carbon material magnetizing method |
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Assignee: Beijing North Xinyuan Electrical Carbon Products Co., Ltd. Assignor: Wuhan Institute of Technology Contract record no.: 2011420000243 Denomination of invention: Method for preparing nano metallic nickel granular material coating with carbon Granted publication date: 20100106 License type: Exclusive License Open date: 20080514 Record date: 20110919 |
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