CN100455383C - Method for preparing carbon-coated metal nano material whose particle diameter is controllable - Google Patents
Method for preparing carbon-coated metal nano material whose particle diameter is controllable Download PDFInfo
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- CN100455383C CN100455383C CNB2006101341899A CN200610134189A CN100455383C CN 100455383 C CN100455383 C CN 100455383C CN B2006101341899 A CNB2006101341899 A CN B2006101341899A CN 200610134189 A CN200610134189 A CN 200610134189A CN 100455383 C CN100455383 C CN 100455383C
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Abstract
The present invention relates to a preparation method of carbon covered metal nano material whose grain size can be controlled. Said method uses spherical micelle made up by using ionic surfactant as template, uses phenol-formaldehyde resin as carbon source, uses transition metal organic compound as metal source, and adopts emulsion polymerization method to prepare precursor body of carbon covered metal nano material, then said precursor body is charred so as to obtain the invented product. Said product can be used as carrier of magnetic catalyst, and can be used for separation, recovery and reutilization of catalyst.
Description
Technical field
The present invention relates to the interleaving techniques field of carbon nano material and metal nano material, particularly relate to the controlled carbon-clad metal preparation of nanomaterials of a kind of particle diameter
Background technology
The carbon-clad metal nano material is a kind of novel nanocarbon-metal composite material, for fullerene carbon green onion is closely wrapped up the brilliant orderly nuclear/shell clad structure that forms of nano metal.Owing to coat the enclosure space that carbon-coating forms the metallic particles that is coated is completely cut off with environment, have great importance for the practical application of environment sensitive metal material.In addition, this composite combines the physicochemical properties and the interior characteristic that belongs to covered with gold leaf of graphitic carbon excellence, therefore in many technical fields such as physics, chemistry, has particularly showed great application prospect in fields such as magnetics, electricity, optics, medical science.
Up to now, scientists has been explored the multiple method for preparing the carbon-clad metal nano material.Wherein, arc discharge method be study the earliest, also be the most frequently used a kind of method.Also have with the similar technology of preparing of arc discharge method: ion beam sputtering, electron beam irradiation method, laser evaporation method, plasma evaporation method etc.The crystallization degree of the product shell carbon of employing arc discharge method preparation is higher, but degree of purity of production is lower, the preparation condition harshness.Chemical vapour deposition technique is a kind of method of fairly simple easy control, be easy to realize fairly large preparation, but need be on substrate even dispersing nanometer level catalyst, the later stage product is more loaded down with trivial details with separating of substrate and catalyst carrier, simultaneously also can the association CNT and accessory substance such as amorphous carbon particle.The low temperature pyrogenation carbonizatin method is suitable for preparing the higher carbon-clad metal nano material of purity, and this method technology is simple, carbonization yield is high, but can't the size and the particle diameter of product be distributed.Other method for example activation annealing and gel explosion method also once was used to the preparation of carbon-clad metal nano material, but the two all follows solid phase charcoal forming machine system, and there is higher danger in the not easy to operate and control of preparation process, extensive synthetic being restricted.
From the development process of the preparation and the application study of carbon-clad metal nano material, the product that obtains high-purity, size homogeneous is its performance of research and the basis of expanding its application.2004, Jang, J. waiting the people is raw material with pyrroles, the spherical micelle of constructing with surfactant is the confinement microreactor, successfully prepares hollow Nano carbon capsule (J.Jang, the X.L.Li and J.H.Oh of high-purity, size homogeneous, ChemicalCommunications, a kind of new method-soft template method of controlled preparation carbon nanomaterial 2004,794.), is provided.After this, by the soft template effect of micella, carbon fiber (J.Jang and J.Bae, AngewandteChemie-International Edition, 2004,43,3803.), magnetic carbon granule (J.Jang and H.Yoon, Small, 2005,1,1195.) and porous carbon materials (F.Q.Zhang, Y.Meng, D.Gu, Y.Yan, C.Z.Yu, B.Tu, D.Y.Zhao, Journal of the American Chemical Society, 2005,127,13508.) also successfully prepared, but also do not had this method is used for the report of controlled preparation carbon-cladded magnetic metal nanometer material so far.
Summary of the invention
The purpose of this invention is to provide a kind of productive rate height, high efficiency preparation method that again can controlled preparation carbon-clad metal nano material simple to operate.
Technical scheme of the present invention realizes by following step: with the ionic surfactant positive micella of constructing sphere soluble in water is the confinement microreactor, add source metal and carbon source, reactant is reacted in micella and form shell/nuclear clad structure, obtain the presoma of described carbon-clad metal nano material, the presoma charing for preparing gained is obtained the carbon-clad metal nano material.
Concrete reactions steps is: the ionic surfactant that earlier with concentration is 2～20mmol/l is soluble in water, treat that it dissolves fully after, add the catalyst of phenol, formaldehyde and phenolic aldehyde polymerisation, fully stirred 30 minutes.The consumption of phenol is every liter of solution 2～20mmol, and the mol ratio of phenol and formaldehyde is 1: 20～60, and catalyst is selected from sodium carbonate or ammonia spirit, and sodium carbonate amount is 0.5～1mmol, and the concentration of ammonia spirit is 0.11mol/l, and consumption is 1～3ml; Drop into transition metal organometallic compound subsequently, ultrasonic processing 30 minutes.The consumption of transition metal organometallic compound is every liter of solution 0.5～20mmol; Gained solution is reaction 1～6h under 60 ℃～95 ℃, obtains the presoma of described carbon-clad metal nano material.The presoma of preparation gained is placed carbide furnace charing 2h under hydrogen atmosphere, obtain the carbon-clad metal nano material, hydrogen flow rate is 15cm
3/ min.
The described related substances of this technical scheme is respectively:
Described ionic surfactant is selected from cationic surfactant hexadecyltrimethylammonium chloride or ammonium bromide, dodecyl or OTAC; Or anion surfactant oleic acid, neopelex, C
12, C
16Or C
18Sodium alkyl sulfate.Described phenol be selected from neighbour-benzenediol ,-benzenediol, right-benzenediol or p-t-butyl phenol a kind of.Described transition metal organometallic compound is selected from that ethanedioic acid is ferrous, ferrocene, cobaltocene, dicyclopentadienyl nickel, carbonyl iron, carbonyl cobalt or carbonyl nickel.
Described charing treatment conditions are: in 450 ℃ and 485 ℃ constant temperature half an hour respectively, with the heating rate of 2 ℃/min temperature is risen to 700～900 ℃ of charings then and handle 2h.
Effect of the present invention and benefit are as follows:
1. be template by the spherical micelle of constructing with surfactant, the preparation of presoma be controlled in the confinement microreactor, and by the conditioned reaction condition to being regulated and control by the particle size of coated particle and distribution.
2. be the presoma of carbon with the phenolic resins that generates behind resorcinol and the oxymethylene polymerization, raw material sources are easy to get, and polymerisation is easy to operate.
3. be a kind of method that adopts the low-temperature carbonization technology to prepare the carbon-coated nano material, by suitable adjusting carbonization heating rate, carbonization temperature and carbonization time, can prepare complete form, coat the high carbon-clad metal nano material of the carbon-coating degree of order.Process is simple, easy to operate, process is amplified easily,
4. prepared carbon-clad metal nano material impurity content is low, do not need purifying.
Description of drawings
Fig. 1 is the low power transmission electron microscope photo of the carbon-encapsulated iron nano material of embodiment 1 gained.
Fig. 2 is the high power transmission electron microscope photo of the carbon-encapsulated iron nano material of embodiment 1 gained.
Fig. 3 is the low power transmission electron microscope photo of the carbon-encapsulated iron nano material of embodiment 2 gained.
Fig. 4 is the low power transmission electron microscope photo of the carbon-encapsulated iron nano material of embodiment 3 gained.
The specific embodiment
Embodiment 1
Take by weighing the 0.2mmol softex kw, join in the small beaker that contains the 100ml deionized water, treat the solution clarification, add the 3mmol resorcinol respectively, 0.12mol formaldehyde and 1.2ml concentration are the ammonia spirit of 0.11mol/l.Fully stir after 30 minutes, adding 0.1mmol ethanedioic acid is ferrous, and ultrasonic processing 30 minutes makes gained solution continue reaction 2.5h in 90 ℃.After reaction finished, with the mother liquor centrifugation, precipitation was with absolute ethyl alcohol and deionized water cyclic washing and centrifugal, at last with the brown product as for dried overnight in 60 ℃ the baking oven.Collect the brown powder of above-mentioned preparation and put into quartz boat, quartz boat is placed the central authorities of the crystal reaction tube in the tubular type retort, carry out carbonization treatment with certain heating rate.Whole carbonisation is to carry out under the hydrogen gas protection, and hydrogen flow rate is 15cm
3/ min.Set furnace temperature simultaneously, make its speed be warmed up to 450 ℃, constant temperature 30min with 10 ℃/min; Heating rate with 2.5 ℃/min rises to 485 ℃, constant temperature 30min then; Be cooled to room temperature after with the heating rate of 2 ℃/min temperature being risen to 900 ℃ of charing 2h at last.After carbonization reaction finished, the black carbide of collecting was carbon iron clad nano material.Transmission electron microscope and high-resolution-ration transmission electric-lens show: carbon-coated nano particle outward appearance is torispherical and has desirable shell nuclear clad structure, coats the about 7～9nm of thickness of carbon-coating, the about 6～7nm of the diameter of coated particle (Fig. 1 and Fig. 2).
Embodiment 2
Take by weighing the 0.2mmol softex kw, join in the small beaker that contains the 100ml deionized water, treat the solution clarification, add the 3mmol resorcinol respectively, 0.12mol formaldehyde and 1.2ml concentration are the ammonia spirit of 0.11mol/l.Fully stir after 30 minutes, adding 0.16mmol ethanedioic acid is ferrous, ultrasonic processing 30 minutes.Stir with after-acceleration, make gained solution continue reaction 2.5h in 90 ℃.After reaction finished, with the mother liquor centrifugation, precipitation was with absolute ethyl alcohol and deionized water cyclic washing and centrifugal, at last with the brown product as for dried overnight in 60 ℃ the baking oven.Collect the brown powder of above-mentioned preparation and put into quartz boat, quartz boat is placed the central authorities of the crystal reaction tube in the tubular type retort, carry out carbonization treatment with certain heating rate.Whole carbonisation is to carry out under the hydrogen gas protection, and hydrogen flow rate is 15cm
3/ min.Set furnace temperature simultaneously, make its speed be warmed up to 450 ℃, constant temperature 30min with 10 ℃/min; Heating rate with 2.5 ℃/min rises to 485 ℃, constant temperature 30min then; Be cooled to room temperature after with the heating rate of 2 ℃/min temperature being risen to 900 ℃ of charing 2h at last.After carbonization reaction finished, the black carbide of collecting was carbon iron clad nano material.The low power transmission electron microscope shows: carbon-coated nano particle outward appearance is torispherical and has desirable shell nuclear clad structure, coats the about 7～11nm of thickness of carbon-coating, the about 8～20nm of the diameter of coated particle (Fig. 3).
Embodiment 3
Take by weighing the 0.2mmol softex kw, join in the small beaker that contains the 100ml deionized water, treat the solution clarification, add the 3mmol resorcinol respectively, 0.12mol formaldehyde and 1.2ml concentration are the ammonia spirit of 0.11mol/l.Fully stir after 30 minutes, adding 0.2mmol ethanedioic acid is ferrous, ultrasonic processing 30 minutes.Stir with after-acceleration, make gained solution continue reaction 2.5h in 90 ℃.After reaction finished, with the mother liquor centrifugation, precipitation was with absolute ethyl alcohol and deionized water cyclic washing and centrifugal, at last with the brown product as for dried overnight in 60 ℃ the baking oven.Collect the brown powder of above-mentioned preparation and put into quartz boat, quartz boat is placed the central authorities of the crystal reaction tube in the tubular type retort, carry out carbonization treatment with certain heating rate.Whole carbonisation is to carry out under the hydrogen gas protection, and hydrogen flow rate is 15cm
3/ min.Set furnace temperature simultaneously, make its speed be warmed up to 450 ℃, constant temperature 30min with 10 ℃/min; Heating rate with 2.5 ℃/min rises to 485 ℃, constant temperature 30min then; Be cooled to room temperature after with the heating rate of 2 ℃/min temperature being risen to 900 ℃ of charing 2h at last.After carbonization reaction finished, the black carbide of collecting was carbon iron clad nano material.The low power transmission electron microscope shows: carbon-coated nano particle outward appearance is torispherical and has desirable shell nuclear clad structure, coats the about 20～25nm of thickness of carbon-coating, the about 35～45nm of the diameter of coated particle (Fig. 4).
Embodiment 4
Take by weighing the 0.2mmol neopelex, join in the small beaker that contains the 100ml deionized water, treat the solution clarification, add the 3mmol resorcinol respectively, 0.12mol formaldehyde and 1.2ml concentration are the ammonia spirit of 0.11mol/l.Fully stir after 30 minutes, adding 0.16mmol ethanedioic acid is ferrous, ultrasonic processing 30 minutes.Stir with after-acceleration, make gained solution continue reaction 2.5h in 90 ℃.After reaction finished, with the mother liquor centrifugation, precipitation was with absolute ethyl alcohol and deionized water cyclic washing and centrifugal, at last with the brown product as for dried overnight in 60 ℃ the baking oven.Collect the brown powder of above-mentioned preparation and put into quartz boat, quartz boat is placed the central authorities of the crystal reaction tube in the tubular type retort, carry out carbonization treatment with certain heating rate.Whole carbonisation is to carry out under the hydrogen gas protection, and hydrogen flow rate is 15cm
3/ min.Set furnace temperature simultaneously, make its speed be warmed up to 450 ℃, constant temperature 30min with 10 ℃/min; Heating rate with 2.5 ℃/min rises to 485 ℃, constant temperature 30min then; Be cooled to room temperature after with the heating rate of 2 ℃/min temperature being risen to 900 ℃ of charing 2h at last.After carbonization reaction finished, the black carbide of collecting was carbon iron clad nano material.
Embodiment 5
Take by weighing the 0.2mmol softex kw, join in the small beaker that contains the 100ml deionized water, treat the solution clarification, add the 3mmol resorcinol respectively, 0.12mol formaldehyde and 1.2ml concentration are the ammonia spirit of 0.11mol/l.Fully stir after 30 minutes, add the 0.1mmol ferrocene, ultrasonic processing 30 minutes.Stir with after-acceleration, make gained solution continue reaction 2.5h in 90 ℃.After reaction finished, with the mother liquor centrifugation, precipitation was with absolute ethyl alcohol and deionized water cyclic washing and centrifugal, at last with the bronzing product as for dried overnight in 60 ℃ the baking oven.Collect the bronzing powder of above-mentioned preparation and put into quartz boat, quartz boat is placed the central authorities of the crystal reaction tube in the tubular type retort, carry out carbonization treatment with certain heating rate.Whole carbonisation is to carry out under the hydrogen gas protection, and hydrogen flow rate is 15cm
3/ min.Set furnace temperature simultaneously, make its speed be warmed up to 450 ℃, constant temperature 30min with 10 ℃/min; Heating rate with 2.5 ℃/min rises to 485 ℃, constant temperature 30min then; Be cooled to room temperature after with the heating rate of 2 ℃/min temperature being risen to 900 ℃ of charing 2h at last.After carbonization reaction finished, the black carbide of collecting was carbon iron clad nano material.
Embodiment 6
Take by weighing the 0.2mmol softex kw, join in the small beaker that contains the 100ml deionized water, treat the solution clarification, add the 3mmol resorcinol respectively, 0.12mol formaldehyde and 1.2ml concentration are the ammonia spirit of 0.11mol/l.Fully stir after 30 minutes, add 0.1mmol eight carbonyl cobalts, ultrasonic processing 30 minutes.Stir with after-acceleration, make gained solution continue reaction 2.5h in 90 ℃.After reaction finished, with the mother liquor centrifugation, precipitation was with absolute ethyl alcohol and deionized water cyclic washing and centrifugal, then as for dried overnight in 60 ℃ the baking oven.Collect product and put into quartz boat, quartz boat is placed the central authorities of the crystal reaction tube in the tubular type retort, carry out carbonization treatment with certain heating rate.Whole carbonisation is to carry out under the hydrogen gas protection, and hydrogen flow rate is 15cm
3/ min.Set furnace temperature simultaneously, make its speed be warmed up to 450 ℃, constant temperature 30min with 10 ℃/min; Heating rate with 2.5 ℃/min rises to 485 ℃, constant temperature 30min then; Be cooled to room temperature after with the heating rate of 2 ℃/min temperature being risen to 900 ℃ of charing 2h at last.After carbonization reaction finished, the black carbide of collecting was carbon bag cobalt nano material.
Claims (5)
1, the controlled carbon-clad metal preparation of nanomaterials of a kind of particle diameter, it is characterized in that this method is earlier is that the ionic surfactant of 2～20mmol/l is soluble in water with concentration, after treating that it dissolves fully, add the catalyst of phenol, formaldehyde and phenolic aldehyde polymerisation, fully stirred 30 minutes; The consumption of phenol is every liter of solution 2～20mmol, and the mol ratio of phenol and formaldehyde is 1: 20～60, and catalyst is selected from sodium carbonate or ammonia spirit, and sodium carbonate amount is 0.5～1mmol, and ammonia spirit concentration is 0.11mol/l, and consumption is 1～3ml; Drop into transition metal organometallic compound subsequently, ultrasonic processing 30 minutes; The consumption of transition metal organometallic compound is every liter of solution 0.5～20mmol; Gained solution is reaction 1～6h under 60～95 ℃, and the novolac polymer that obtains is as the presoma of carbon; At last presoma is placed retort, carry out charing and handle under hydrogen atmosphere, obtain the carbon-clad metal nano material, hydrogen flow rate is 15cm
3/ min.
2, the controlled carbon-clad metal preparation of nanomaterials of a kind of particle diameter as claimed in claim 1 is characterized in that it is hexadecyltrimethylammonium chloride or ammonium bromide, dodecyl or OTAC that the described ionic surfactant of this method is selected from cationic surfactant; Or anion surfactant is oleic acid, neopelex, C12, C16 or C18 sodium alkyl sulfate.
3, the controlled carbon-clad metal preparation of nanomaterials of a kind of particle diameter as claimed in claim 1 is characterized in that the transition metal organometallic compound described in this method is selected from that ethanedioic acid is ferrous, ferrocene, cobaltocene, dicyclopentadienyl nickel, carbonyl iron, carbonyl cobalt or carbonyl nickel.
4, the controlled carbon-clad metal preparation of nanomaterials of a kind of particle diameter as claimed in claim 1, it is characterized in that the phenol described in this method be selected from neighbour-benzenediol ,-benzenediol, right-benzenediol or p-t-butyl phenol.
5, the controlled carbon-clad metal preparation of nanomaterials of a kind of particle diameter as claimed in claim 1, it is characterized in that the charing treatment conditions described in this method are:, with the heating rate of 2 ℃/min temperature is risen to 700～900 ℃ of charings then and handled 2 hours in 450 ℃ and 485 ℃ constant temperature half an hour respectively.
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| CN102717070A (en) * | 2012-07-10 | 2012-10-10 | 四川大学 | Method for preparing carbon-coated copper nano particles through liquid alkane reflux method |
| CN107617736A (en) * | 2017-09-08 | 2018-01-23 | 张家港创博金属科技有限公司 | Metal-resin composite pellets preparation method and device |
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