CN101728045A - Cobalt oxide/carbon composite nano wave-absorbing material and preparation method thereof - Google Patents
Cobalt oxide/carbon composite nano wave-absorbing material and preparation method thereof Download PDFInfo
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- CN101728045A CN101728045A CN200910112780A CN200910112780A CN101728045A CN 101728045 A CN101728045 A CN 101728045A CN 200910112780 A CN200910112780 A CN 200910112780A CN 200910112780 A CN200910112780 A CN 200910112780A CN 101728045 A CN101728045 A CN 101728045A
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Abstract
The invention discloses a cobalt oxide/carbon composite nano wave-absorbing material and a preparation method thereof and relates to a magnet/dielectric composite nano wave-absorbing material. The cobalt oxide/carbon composite nano wave-absorbing material has a core-shell structure, wherein the core is magnetic cobalt oxide; and the shell is a carbon layer. The preparation method comprises: adding a cobalt salt into a solvent, and after the cobalt salt is dissolved, filling the solution into a reaction kettle; placing the reaction kettle in an outer cover and heating the reaction kettle; after the reaction kettle cools naturally to room temperature, taking out supernatant liquor, carrying out centrifugal separation on lower precipitate, washing and drying the precipitate to obtain a flaky/flower-shaped cobalt hydroxide precursor; mixing the precursor and oleylamine in a quartz tube; after the precursor is dissolved, inserting the quartz tube in a tubular furnace to heat the quartz tube at a constant temperature for at least 20 minutes; and taking out the quartz tube, adding absolute ethanol, standing the mixture, carrying out centrifugal separation on the mixture, and washing and drying the precipitate to obtain the cobalt oxide/carbon magnet/dielectric composite nano wave-absorbing material.
Description
Technical field
The present invention relates to a kind of ferromagnetic/the dielectric composite nano wave-absorbing material, especially relating to a kind of amorphous carbon or graphitic carbon that is kernel to have ferromagnetic cobalt oxide, has a dielectricity is core/shell type composite nano wave-absorbing material of shell and preparation method thereof.
Background technology
Absorbing material has a wide range of applications in military field, has become the key of various countries' military equipment stealth technology research; And along with the development of electronics industry, the harm of electromagnetic radiation is serious day by day, electromagnetic radiation has become the 4th pollutant sources after air pollution, water pollution and noise pollution, biological environment and health have been caused serious harm, and using absorbing material is the effective way that solves electromagnetic pollution harm.Therefore the research to absorbing material has very important significance.Desirable absorbing material should have characteristics such as strong absorption, wideband section, thin thickness and light weight, and in order to satisfy these requirements better, preparation novel nano composite wave-suction material becomes current research focus.
State of development from present absorbing material, one type material is difficult to satisfy the composite request of " thin, light, wide, strong " that stealth technology proposed of improving day by day, dielectric type absorbing material and the main coverage of magnetic absorbing material are respectively at the low side of superhigh frequency band and high-end, therefore multiple absorbing material need be carried out compound best stealth effect, the raising absorbing property of obtaining of various ways.The nano combined two-phase absorbing material of ferromagnetic/dielectric has comprehensively been brought into play the excellent properties of two kinds of materials.In addition, exist a large amount of heterogeneous interfaces in ferromagnetic/dielectric composite construction, can produce electromagnetic consumable mechanism such as multiple refraction-multiple absorption and interfacial polarization, so ferromagnetic/dielectric nano composite material has huge development space and good prospects for application.Ferromagnetic/the dielectric nano composite material, as α-Fe/Fe
3B/Y
2O
3Composite particles, Fe/CNT etc. have demonstrated outstanding absorbing property, though because the individual layer absorbing material that contains heterogeneous wave-absorber is optimal absorbing material, if will directly obtain, from principle and technical all be very difficult.
In the research in present this field, mainly by vapour deposition (Che, R.C.; Peng, L.M.; Duan, X.F.Microwave absorption enhancement and complex permittivity and permeability of Fe encapsulatedwithin carbon nanotubes[J] .Adv.Mater, 401.), arc discharge (Liu, X.G. 2004,16 (5):; Geng, D.Y.; Zhang.Z.D.Microwave-absorption properties of ZnO-coated iron nanocapsules[J] .Appl.Phys.Lett, 2008,92:1731171.), heat treatment-ball milling (Liu, J.R.; Itoh, M.; Machida.K.I.Elecrtomagnetic waveabsorption properties of α-Fe/Fe
3B/Y
2O
3Nanocomposites in gigahertz range[J] .Appl.Phys.Lett, 2000,4017.) etc. 83 (19): method prepares ferromagnetic/dielectric nano composite material, these method complex process, reaction condition is harsh relatively, operating process is loaded down with trivial details relatively, and productive rate is lower, thereby has been subjected to restriction to a certain degree in actual applications.
Summary of the invention
The purpose of this invention is to provide a kind of cobalt oxide/carbon composite nano absorbing material and preparation method thereof.
Cobalt oxide of the present invention/carbon composite nano absorbing material is a nucleocapsid structure, and kernel is a ferromagnetism cobalt oxide kernel, and shell is a carbon-coating, and kernel is coated in the shell; Described ferromagnetism cobalt oxide kernel is the cobalt oxide nano particle, or nanometer sheet, or the aggregation that is made of nano particle or nanometer sheet, and the particle diameter of described ferromagnetism cobalt oxide kernel is 10～300nm; Described carbon-coating is an amorphous carbon layer, or the graphite carbon-coating, or amorphous carbon and graphitic carbon mixing carbon-coating, and the thickness of described carbon-coating is 1～100nm.
The preparation method of cobalt oxide of the present invention/carbon composite nano absorbing material may further comprise the steps:
1) cobalt salt is added in the solvent, after the cobalt salt dissolving, in the reactor of packing into;
2) reactor is packed into overcoat, heating;
3) after the question response still naturally cools to room temperature, take out supernatant liquor, the centrifugation lower sediment is cleaned, and oven dry promptly gets sheet/flower-shaped cobalt hydroxide predecessor.
4) in quartz ampoule, predecessor is mixed with oleyl amine, the dissolving back is inserted quartz ampoule in the tube furnace and is heated, constant temperature behind the 20min takes out quartz ampoule at least, add absolute ethyl alcohol, leave standstill, the centrifugation precipitation, dry after the washing and precipitating, promptly get cobalt oxide/carbon ferromagnetic/the dielectric composite nano wave-absorbing material, this product be a kind of ferromagnetic/the dielectric composite nano materials, kernel is for having ferromagnetic cobalt oxide kernel, and shell is to have the amorphous carbon layer of dielectricity or the mixed layer of graphite carbon-coating and amorphous carbon and graphitic carbon, and kernel is coated in the shell.
In step 1), described cobalt salt preferably is selected from a kind of in cobalt nitrate, cobalt chloride, the cobalt acetate etc.; Described alcohol preferably is selected from a kind of in ethanol, normal propyl alcohol, n-butanol, the n-amyl alcohol etc.; Described hydramine preferably is selected from a kind of in monoethanolamine, diethanol amine, the triethanolamine etc.; Described solvent is preferably water, pure and mild hydramine mixed solvent, and by volume, water: alcohol: hydramine can be 20: (1～20): (1～20) is preferably 10: 5: 4.
In step 2) in, the temperature of described heating can be 170～200 ℃, but constant temperature 2h at least after the heating; The temperature of described heating is preferably 180 ℃, and the heating back is constant temperature 12h preferably.
In step 3), described cleaning preferably successively water and ethanol clean repeatedly at least 3 times, the temperature of described oven dry is preferably 80 ℃.
In step 4), the consumption of described predecessor and oleyl amine, by volume, predecessor: oleyl amine can be 1: (25～50), and predecessor: oleyl amine is preferably 1: 25, ultrasonic dissolution is preferably adopted in described dissolving, the temperature of described heating can be 260～350 ℃, is preferably 300 ℃, and the time of described constant temperature is preferably 20min, described cleaning is preferably cleaned 1 time with cyclohexane and absolute ethyl alcohol successively repeatedly at least, and the temperature of described oven dry is preferably 80 ℃.
The present invention carries out solvent thermal reaction by inorganic cobalt salt is dissolved in the mixed solvent, obtains the predecessor of nanoscale, and heat treatment in organic amine then obtains the product that the surface has coated carbon-coating equably, has formed ferromagnetic/dielectric composite nano wave-absorbing material.With respect to the preparation method of the ferromagnetic/dielectric composite nano wave-absorbing material of present report and the carbon method for coating on the surface, outstanding advantage of the present invention is:
What 1) the present invention adopted is a kind of simple liquid chemical method, have easy and simple to handle, condition and be easy to characteristics such as control, and at present the preparation method of the ferromagnetic/dielectric composite nano wave-absorbing material of bibliographical information mainly based on vapour deposition process (needing the accurate conditions such as air-flow in the preparation process, air pressure of strictly controlling), by contrast, condition and range of the present invention is looser.
2) at present the method for the coated with carbon of report need be through multistep operations such as the hydrolysis of glucose, high-temperature heat treatment, and to the strictness of required conditions such as hydrolysis pH value, heat treatment temperature, and the present invention is in the process of carbon coated, and conditions needed is simple.
3) product productive rate height of the present invention, and with respect to the high temperature of vapour deposition more than 1000 ℃, mild condition of the present invention, this can be large-scale production and reduces cost.
4) because the prepared cobalt oxide of the present invention/carbon composite nano absorbing material adopts ferromagnetic material and dielectric material compound, therefore not only have loose structure, and have excellent absorbing property, can satisfy the actual needs of the relevant military project and the product for civilian use.
Description of drawings
Fig. 1 is the SEM figure of the predecessor of the embodiment of the invention.In Fig. 1, the gained predecessor is that cabaltous nitrate hexahydrate adds (water: ethanol: diethanol amine=20: 10: 1) in the mixed solvent that entry, ethanol and diethanol amine form under magnetic agitation, after treating to dissolve fully, the solution reactor of packing into is heated to 180 ℃, keeps obtaining behind the 12h; Predecessor is a sheet, and thickness is 10～50nm, and size is about 300nm.
Fig. 2 is the product S EM figure that the predecessor of the embodiment of the invention after heat treatment obtains.As seen from Figure 2, product has still kept the laminated structure of predecessor well.
Fig. 3 is the HRTEM figure of single sheet product.In Fig. 3, wherein several groups of interplanar distances have been measured, 0.087nm=d
CoO (422), 0.212nm=d
CoO (200), 0.113nm=d
CoO (400),, determine that it is CoO (JCPDS43-1004), space group Fm-3m, cell parameter according to these d values
Fig. 4 is the high resolution picture of sheet product marginal portion.In Fig. 4, select the outermost layer place to measure interplanar distance, 0.359nm is corresponding to the crystal face of graphitic carbon (JCPDS 02-0456); Visible exterior has coated the thick carbon-coating of 1～5nm, and graphitization takes place the existing part of carbon-coating.
Fig. 5 is the magnetic hysteresis loop of sheet product under low temperature (2K) and room temperature (300K).In Fig. 5, abscissa is magnetic field intensity H[T], ordinate is M (magnetization) [emu/g]; ■ is 2K, ● be 300K; Can see that product all demonstrates ferromagnetism when 2K and 300K.
Fig. 6 is a ZFC-FC curve under the sheet product 200Oe.In Fig. 6, ordinate is M (magnetization) [emu/g]; is ZFC (null field cooling), and zero is FC (cooling); The phase transition temperature of product is very high, about 300K; Abscissa is temperature T [K].
Fig. 7 inhales the three-dimensional cloud atlas of ripple for the sheet product.In Fig. 7, the loss of sheet product maximum reflection is 55dB; Abscissa is frequency Frequency (G Hz), and left ordinate is thickness T hickness (mm), right ordinate be reflection loss Reflectloss (dB).
Fig. 8 is that ripple figure is inhaled at the single thickness place of sheet product.In Fig. 8, abscissa is frequency Frequency (G Hz), ordinate be reflection loss Reflectloss (dB); Inhaling the thickness that the ripple curve represents respectively from left to right is 3mm, 2.5mm, 2mm, 4.496mm; The sheet product is at thickness 4.496mm, and frequency 16.41GHz place reaches maximum reflection loss 55dB.
Fig. 9 is the SEM figure of the predecessor of the embodiment of the invention.In Fig. 9, predecessor is that cabaltous nitrate hexahydrate adds in the mixed solvent that entry, ethanol and diethanol amine form (water: ethanol: diethanol amine=20: 10: 8), the solution reactor of packing into is heated to 180 ℃, keeps obtaining behind the 12h under magnetic agitation; Predecessor is the flower-shaped thing that is self-assembled into by sheet as shown in the figure, and size is about 2m, and is dispersed fine.
The product S EM figure that Figure 10 after heat treatment obtains for predecessor.In Figure 10, product still keeps the flower-like structure of predecessor well, but the surface becomes coarse by smooth.
Figure 11 is the TEM figure of single flower-shaped product.In Figure 11, can be clear that coating has all taken place on the surface of every flower.
Figure 12 is the HRTEM figure of flower-shaped product marginal portion.In Figure 12, can see that the carbon-coating thickness of coating is about 100nm.
Figure 13 is the magnetic hysteresis loop of flower-shaped product under low temperature (2K) and room temperature (300K).In Figure 13, abscissa is magnetic field intensity H[T], ordinate is M (magnetization) [emu/g]; ■ is 2K, ● be 300K; Can see that product all is different from the antiferromagnetism of general CoO when 2K and 300K, but demonstrate ferromagnetism.
Figure 14 is a ZFC-FC curve under the flower-shaped product 200Oe.In Figure 14, abscissa is temperature T [K], and ordinate is M (magnetization) [emu/g]; is ZFC (null field cooling), and zero is FC (cooling); The phase transition temperature of product is very high, about 300K.
Figure 15 is that flower-shaped product is inhaled the three-dimensional cloud atlas of ripple.In Figure 15, abscissa is frequency Frequency (G Hz), and left ordinate is thickness T hickness (mm), right ordinate be reflection loss Reflectloss (dB); Flower-shaped product maximum reflection loss 40dB.And when thickness 2.5mm was following, flower-shaped product can reach the absorption more than the 10dB in 8～18GHz band limits, in 10～15GHz scope internal reflection loss value greater than 30dB.
Figure 16 is that ripple figure is inhaled at the single thickness place of flower-shaped product.In Figure 16, abscissa is frequency Frequency (G Hz), ordinate be reflection loss Reflectloss (dB); Inhaling the thickness that the ripple curve represents respectively from left to right is 3.0mm, 2.5mm, 2.398mm, 2.0mm; At thickness 2.4mm, frequency 12.79GHz place reaches maximum reflection loss value 40dB.
Embodiment
The invention will be further described in conjunction with figure below by embodiment.
Embodiment 1
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, ethanol and the diethanol amine of 31mL form (water: ethanol: diethanol amine=20: 10: 1), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain hydroxide flake cobalt precursor thing.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
Predecessor and product carry out systematic research through modern nanometer test and analysis technologies such as SEM, TEM, HRTEM to its pattern, composition, micro-structural, and product has used the SQUID magnetometer to carry out magnetic characterization, and the network vector analyzer carries out the absorbing property analysis.SEM characterizes as illustrated in fig. 1 and 2, and predecessor and product are laminated structure, and diameter is about 300nm.Choose single tablet it is carried out the high resolution picture analysis, Fig. 3 and 4 is the HRTEM figure of in the middle of the selected sheet product and marginal portion, determines that it is CoO (JCPDS 43-1004), space group Fm-3m, cell parameter by measuring interplanar distance at mid portion
After oleyl amine heat treatment, the products therefrom surface is coated with the thick carbon-coating of 1-5nm.
Fig. 5 and 6 is magnetic characterization of product, can see that resulting product has strong ferromagnetism, and it all demonstrates ferromagnetism and has higher phase transition temperature when 2K and 300K.
Fig. 7 and 8 is that the absorbing property of product characterizes, and can see resulting product as dielectric/ferromagnetic composite nano wave-absorbing material, and it is at thickness 4.5mm, and frequency 16.41GHz place reaches maximum reflection loss 55dB, has excellent absorbing property.
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, ethanol and the diethanol amine of 38mL form (water: ethanol: diethanol amine=20: 10: 8), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain flower-shaped cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
SEM characterizes as shown in Figures 9 and 10, and predecessor and product are the flower-shaped thing that the sheet of serving as reasons is formed, and size is about 2um.Choose single flower-shaped thing it is carried out the high resolution picture analysis, Figure 11 and 12 is the HRTEM figure of selected flower-shaped product and marginal portion, can be clearly seen that by the TEM figure of flower-shaped product and the high resolution picture of marginal portion carbon-coating all coats the surface of every flower, carbon-coating thickness is about 100 nanometers.
Figure 13 and 14 is the magnetic characterization of product, can see that resulting product has strong ferromagnetism, and it all demonstrates ferromagnetism and has higher phase transition temperature when 2K and 300K.
Figure 15 and 16 is that the absorbing property of product characterizes, can see that resulting product is as dielectric/ferromagnetic composite nano wave-absorbing material, when thickness 2.5mm is following, in 8～18GHz band limits, can reach the absorption more than the 10dB, in 10～15GHz scope internal reflection loss value greater than 30dB.At thickness 2.4mm, frequency 12.79GHz place reaches maximum reflection loss value 40dB.This shows that resulting product work has excellent absorbing property.
Embodiment 3
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, ethanol and the diethanol amine of 31mL form (water: ethanol: diethanol amine=20: 1: 10), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 60min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, ethanol and the diethanol amine of 38mL form (water: ethanol: diethanol amine=20: 10: 8), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 170 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, ethanol and the diethanol amine of 38mL form (water: ethanol: diethanol amine=20: 10: 8), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 200 ℃ in the baking oven, keeps 2h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, ethanol and the diethanol amine of 31mL form (water: ethanol: diethanol amine=20: 1: 10), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 50 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 45min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
Embodiment 7
(1) takes by weighing 0.3g CoCl
26H
2O, under magnetic agitation, add in the mixed solvent that water, ethanol and the diethanol amine of 31mL form (water: ethanol: diethanol amine=20: 1: 10), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 260 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
(1) takes by weighing 0.3g CoAc
24H
2O, under magnetic agitation, add in the mixed solvent that water, ethanol and the diethanol amine of 32mL form (water: ethanol: diethanol amine=20: 1: 20), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 360 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, ethanol and the monoethanolamine of 38mL form (water: ethanol: monoethanolamine=20: 20: 8), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, ethanol and the triethanolamine of 38mL form (water: ethanol: triethanolamine=20: 10: 8), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
Embodiment 11
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, normal propyl alcohol and the diethanol amine of 38mL form (water: normal propyl alcohol: diethanol amine=20: 10: 8), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, n-butanol and the diethanol amine of 38mL form (water: n-butanol: diethanol amine=20: 10: 8), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
Embodiment 13
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, n-amyl alcohol and the diethanol amine of 38mL form (water: n-amyl alcohol: diethanol amine=20: 10: 8), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, normal propyl alcohol and the monoethanolamine of 38mL form (water: normal propyl alcohol: monoethanolamine=20: 10: 8), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
Embodiment 15
(1) takes by weighing 0.3g Co (NO
3)
26H
2O, under magnetic agitation, add in the mixed solvent that water, n-butanol and the triethanolamine of 38mL form (water: n-butanol: triethanolamine=20: 10: 8), after treating to dissolve fully, with the solution polytetrafluoroethylene reactor of packing into.
(2) reactor is packed into stainless steel outer sleeve is put in and is heated to 180 ℃ in the baking oven, keeps 12h.
(3) after the question response still naturally cools to room temperature, take out and pour out supernatant liquor, the centrifugation lower sediment is cleaned 3 times with absolute ethyl alcohol, and 80 ℃ of oven dry promptly obtain the cobalt hydroxide predecessor.
(4) in quartz ampoule, predecessor and oleyl amine were mixed in 1: 25 by volume, ultrasonic dissolution, then quartz ampoule is inserted in the vertical tube furnace and be heated to 300 ℃ rapidly, behind the 30min quartz ampoule is taken out, add absolute ethyl alcohol and leave standstill, the centrifugation precipitation is used cyclohexane/absolute ethyl alcohol washing and precipitating repeatedly, 80 ℃ of oven dry promptly obtain target product.
Claims (10)
1. cobalt oxide/carbon composite nano absorbing material is characterized in that being nucleocapsid structure, and kernel is a ferromagnetism cobalt oxide kernel, and shell is a carbon-coating, and kernel is coated in the shell; Described ferromagnetism cobalt oxide kernel is the cobalt oxide nano particle, or nanometer sheet, or the aggregation that is made of nano particle or nanometer sheet, and the particle diameter of described ferromagnetism cobalt oxide kernel is 10～300nm; Described carbon-coating is an amorphous carbon layer, or the graphite carbon-coating, or amorphous carbon and graphitic carbon mixing carbon-coating, and the thickness of described carbon-coating is 1～100nm.
2. the preparation method of cobalt oxide as claimed in claim 1/carbon composite nano absorbing material is characterized in that may further comprise the steps:
1) cobalt salt is added in the solvent, after the cobalt salt dissolving, in the reactor of packing into;
2) reactor is packed into overcoat, heating;
3) after the question response still naturally cools to room temperature, take out supernatant liquor, the centrifugation lower sediment is cleaned, and oven dry promptly gets sheet/flower-shaped cobalt hydroxide predecessor;
4) in quartz ampoule, predecessor is mixed with oleyl amine, the dissolving back is inserted quartz ampoule in the tube furnace and is heated, constant temperature behind the 20min takes out quartz ampoule at least, add absolute ethyl alcohol, leave standstill, the centrifugation precipitation, dry after the washing and precipitating, promptly get cobalt oxide/carbon ferromagnetic/the dielectric composite nano wave-absorbing material, this product be a kind of ferromagnetic/the dielectric composite nano materials, kernel is for having ferromagnetic cobalt oxide kernel, and shell is to have the amorphous carbon layer of dielectricity or the mixed layer of graphite carbon-coating and amorphous carbon and graphitic carbon, and kernel is coated in the shell.
3. the preparation method of cobalt oxide as claimed in claim 2/carbon composite nano absorbing material is characterized in that in step 1), and described cobalt salt is selected from a kind of in cobalt nitrate, cobalt chloride, the cobalt acetate.
4. the preparation method of cobalt oxide as claimed in claim 2/carbon composite nano absorbing material is characterized in that in step 1), and described alcohol is selected from a kind of in ethanol, normal propyl alcohol, n-butanol, the n-amyl alcohol;
5. the preparation method of cobalt oxide as claimed in claim 2/carbon composite nano absorbing material is characterized in that in step 1), and described hydramine is selected from a kind of in monoethanolamine, diethanol amine, the triethanolamine;
6. the preparation method of cobalt oxide as claimed in claim 2/carbon composite nano absorbing material, it is characterized in that in step 1) described solvent is water, pure and mild hydramine mixed solvent, by volume, water: alcohol: hydramine is 20: (1～20): (1～20) is preferably 10: 5: 4.
7. the preparation method of cobalt oxide as claimed in claim 2/carbon composite nano absorbing material is characterized in that in step 2) in, the temperature of described heating is 170～200 ℃, heating back constant temperature is 2h at least; The temperature of described heating is preferably 180 ℃, and the heating back is constant temperature 12h preferably.
8. the preparation method of cobalt oxide as claimed in claim 2/carbon composite nano absorbing material is characterized in that in step 3), and described cleaning water and ethanol is successively cleaned 3 times repeatedly at least, and the temperature of described oven dry is 80 ℃.
9. the preparation method of cobalt oxide as claimed in claim 2/carbon composite nano absorbing material is characterized in that in step 4), the consumption of described predecessor and oleyl amine, and by volume, predecessor: oleyl amine is 1: 25～50, and predecessor: oleyl amine is preferably 1: 25.
10. the preparation method of cobalt oxide as claimed in claim 2/carbon composite nano absorbing material, it is characterized in that in step 4), described dissolving is to adopt ultrasonic dissolution, the temperature of described heating is 260～350 ℃, be preferably 300 ℃, the time of described constant temperature is 20min, and described cleaning is to clean repeatedly at least 1 time with cyclohexane and absolute ethyl alcohol successively, and the temperature of described oven dry is 80 ℃.
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