CN106334522A - Graphene oxide-based ferriferrous oxide nanocomposite and preparation method thereof - Google Patents
Graphene oxide-based ferriferrous oxide nanocomposite and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a graphene oxide-based ferriferrous oxide nanocomposite, comprising the following steps: S1) mixing a graphene oxide and a ferrous salt solution to obtain a precursor mixed liquor; S2) regulating pH value to a value which is higher than 8 by adding a first alkaline substance into the above precursor mixed liquor, and reacting to obtain a first reaction solution; S3) mixing the first reaction solution and a pyrrolidone compound, and reacting to obtain a second reaction solution; S4) regulating pH value to a value which is greater than 11 by adding a second alkaline substance into the second reaction solution, and reacting to obtain a third reaction solution; and S5) mixing the third reaction solution and a ammonium bromide surfactant, and reacting to obtain the graphene oxide-based ferriferrous oxide nanocomposite. By preparing crystal nucleus of ferriferrous oxide through a liquid precipitation method and then adding the surfactant for in-situ growth of crystal, the graphene oxide-based ferriferrous oxide nanocomposite is prepared under the conditions of low temperature and normal pressure.
Description
Technical field
The invention belongs to technical field of composite materials, more particularly, to a kind of graphite oxide thiazolinyl ferriferrous oxide nano is combined
Material and preparation method thereof.
Background technology
With the development of modern science and technology progress, various electronic equipments become the necessary article of service human society.However, electronics,
The electromagnetic radiation producing in electrical equipment work process and electromagnetic interference problem govern production and the life of people again, cause people
The deterioration further of class living environment.
At present, electromagnetic wave becomes a kind of new polluter having larger hazardness and being difficult protection, and it not only affects to lead to
News signal and seriously threaten the health of the mankind, and absorbing material due to the electromagnetic wave energy projecting its surface can be absorbed thus
It is developed.Meanwhile, absorbing material also has a wide range of applications in military stealth technology, and therefore, new absorbing material needs
There is in electromagnetic regime as wide as possible excellent electro-magnetic wave absorption ability, simultaneously thickness of thin to be had concurrently, absorption frequency range
Width, light weight and the high characteristic of intensity.
Graphene is a kind of new carbon being made up of single carbon atom close-packed arrays, and it has larger specific surface
Long-pending, good electric heating conductive performance.Meanwhile, Graphene has very high dielectric constant, is easy to polarized in external electromagnetic field
Produce dielectric loss.Ferroso-ferric oxide is a kind of typical magnetic loss consumption material, due to quantum size effect, ferriferrous oxide nano
The size of granule has very important impact to its electromagnetic performance.Because absorbing material has higher wanting to the impedance matching of material
Ask, that is, the dielectric constant of composite and pcrmeability are close.Therefore, for meeting the high-k of Graphene, prepare big chi
Very little ferriferrous oxide particles become trend.Surface of graphene oxide is not reduced and there is oxygen-containing group in a large number, using its table
The oxygen-containing group in face, as the target spot being combined with nano material, graphene oxide is combined with ferroso-ferric oxide, can make electricity
Magnetic wave is subject to the obstruction of space steric effect to delay being directed through of electromagnetic wave after penetrating composite, the high dielectric of graphene oxide
Loss and the high magnetic loss of ferroso-ferric oxide are so that composite has excellent electromagnetic wave absorption performance.
Conventional solvents full-boiled process prepares graphene-based ferriferrous oxide nano composite to be needed for aqueous phase Graphene to go to second
In the high boiling solvents such as glycol, commutation process is loaded down with trivial details and completely can not remove water, through courses of reaction such as High Temperature High Pressure, operates
Danger coefficient is high, and is difficult to prepare with scale.
The Chinese patent of Publication No. cn104923161a discloses a kind of preparation method of magnetic oxygenated Graphene and answers
With synthesizing graphene oxide using improved hummers method, being pressed ferroferric oxide nano granules by coprecipitation certain
Proportional load is in graphene oxide layer, but between the composite graphene sheet layer of its preparation, serious accumulation is overlapping, dispersion
Property is bad, is unfavorable for the raising of Radar Absorbing Properties of Composites.
Content of the invention
In view of this, the technical problem to be solved is to provide a kind of graphite oxide thiazolinyl ferroso-ferric oxide to receive
Nano composite material and preparation method thereof, the method is simple and the graphite oxide thiazolinyl ferriferrous oxide nano composite tool that obtains
There is preferable absorbing property.
The invention provides a kind of preparation method of graphite oxide thiazolinyl ferriferrous oxide nano composite, comprising:
S1) graphene oxide solution is mixed with ferrous salt solution, obtain presoma mixed liquor；
S2) add the first alkaline matter to adjust ph value in described presoma mixed liquor and be more than 8, after reaction, obtain first
Reactant liquor；
S3) described first reactant liquor is mixed with pyrrolidones, after reaction, obtain the second reactant liquor；
S4) add the second alkaline matter to adjust ph value in described second reactant liquor and be more than 11, after reaction, obtain the 3rd anti-
Answer liquid；
S5) described 3rd reactant liquor is mixed with ammonium bromide class surfactant, after reaction, obtain graphite oxide thiazolinyl four
Fe 3 O nano composite material.
Preferably, the mass concentration of described graphene oxide solution is 0.05%～0.6%；The rubbing of described ferrous salt solution
Your concentration is 0.1～0.6mol/l.
Preferably, described pyrrolidones are 2-Pyrrolidone and/or n- methyl pyrrolidone；Described ammonium bromide
Class surfactant is in cetyl trimethylammonium bromide, Dodecyl trimethyl ammonium chloride and benzyl triethyl ammonium bromide
One or more.
Preferably, described pyrrolidones are mixed with the first reactant liquor in the form of pyrrolidones solution
Close；In described pyrrolidones solution, the concentration of pyrrolidones is 0.01～0.1mol/l；
Described ammonium bromide class surfactant is mixed with the 3rd reactant liquor in the form of ammonium bromide class surfactant solution；
In described ammonium bromide class surfactant solution, the concentration of ammonium bromide class surfactant is 0.01～0.05mol/l.
Preferably, described ferrous salt solution, pyrrolidones solution and ammonium bromide surfactant solution plus
Enter speed and be each independently 0.1～0.5ml/s.
Preferably, the mass ratio of the graphene oxide in described graphene oxide solution and the ferrous salt in ferrous salt solution
For 1:(1～5)；
Described pyrrolidones are 1:(1～10 with the mass ratio of ferrous salt in ferrous salt solution)；Described bromination
Ammonium class surfactant is 1:(1～5 with the mol ratio of pyrrolidones).
Preferably,
Described step s1) mix under ultrasound condition；The time of described mixing is 20～40min
Described step s2) reaction temperature be 50 DEG C～70 DEG C；The time of reaction is 20～40min；
Described step s3) in reaction temperature be 75 DEG C～95 DEG C；The time of reaction is 20～40min；
Described step s4) in reaction temperature be 75 DEG C～95 DEG C；The time of reaction is 20～40min；
Described step s5) in reaction temperature be 75 DEG C～95 DEG C；The time of reaction is 160～300min.
Preferably, described first alkaline matter and the second alkaline matter are each independently ammonia, sodium hydroxide and hydrogen-oxygen
Change one or more of potassium.
Preferably, described second alkaline matter is ammonia and sodium hydroxide；Described sodium hydroxide with the mol ratio of ammonia is
1:(1～3).
Present invention also offers a kind of graphite oxide thiazolinyl ferriferrous oxide nano composite.
The invention provides a kind of preparation method of graphite oxide thiazolinyl ferriferrous oxide nano composite, comprising: s1)
Graphene oxide solution is mixed with ferrous salt solution, obtains presoma mixed liquor；S2) add in described presoma mixed liquor
First alkaline matter adjusts ph value and is more than 8, after reaction, obtains the first reactant liquor；S3) by described first reactant liquor and ketopyrrolidine
Class compound mixes, and after reaction, obtains the second reactant liquor；S4 the second alkaline matter) is added to adjust in described second reactant liquor
Ph value is more than 11, after reaction, obtains the 3rd reactant liquor；S5) described 3rd reactant liquor is mixed with ammonium bromide class surfactant,
After reaction, obtain graphite oxide thiazolinyl ferriferrous oxide nano composite.Compared with prior art, the present invention is sunk by liquid phase
Shallow lake method prepares the nucleus of graphite oxide thiazolinyl ferroso-ferric oxide, is subsequently adding surfactant growth in situ crystal, normal in low temperature
Graphite oxide thiazolinyl ferriferrous oxide nano composite is prepared, without High Temperature High Pressure ring in preparation process under the conditions of pressure
Border, effectively reduces energy loss and cost, without solvent commutation, effectively reduces processing step, and improve composite
Dispersibility；And, ferroso-ferric oxide grows on graphene oxide two sides, in obvious coaggregant structure, so that oxidation stone
Black alkene is good with ferroso-ferric oxide associativity, does not reunite between graphene oxide layer, and then makes graphite oxide thiazolinyl four aoxidize three
Ferrum nano composite material has excellent absorbing property.
The present invention preparation graphite oxide thiazolinyl ferriferrous oxide nano composite absorbing property maximum wash after up to-
35.2db.
Brief description
Fig. 1 is that the preparation flow of graphite oxide thiazolinyl ferriferrous oxide nano composite in the embodiment of the present invention 1 is illustrated
Figure；
Fig. 2 is that the x of the graphite oxide thiazolinyl ferriferrous oxide nano composite obtaining in the embodiment of the present invention 1～3 penetrates
Line diffraction spectrogram；
Fig. 3 is the stereoscan photograph of the graphite oxide thiazolinyl ferriferrous oxide nano composite obtaining in embodiment 1；
Fig. 4 is the transmission electricity of the graphite oxide thiazolinyl ferriferrous oxide nano composite obtaining in the embodiment of the present invention 1
Mirror photo；
Fig. 5 is the suction ripple of the graphite oxide thiazolinyl ferriferrous oxide nano composite obtaining in the embodiment of the present invention 1～3
Performance chart.
Specific embodiment
The invention provides a kind of preparation method of graphite oxide thiazolinyl ferriferrous oxide nano composite, comprising: s1)
Graphene oxide solution is mixed with ferrous salt solution, obtains presoma mixed liquor；S2) add in described presoma mixed liquor
First alkaline matter adjusts ph value and is more than 8, after reaction, obtains the first reactant liquor；S3) by described first reactant liquor and ketopyrrolidine
Class compound mixes, and after reaction, obtains the second reactant liquor；S4 the second alkaline matter) is added to adjust in described second reactant liquor
Ph value is more than 11, after reaction, obtains the 3rd reactant liquor；S5) described 3rd reactant liquor is mixed with ammonium bromide class surfactant,
After reaction, obtain graphite oxide thiazolinyl ferriferrous oxide nano composite.
Wherein, the present invention is not particularly limited to the source of all raw materials, can be alternatively commercially available for self-control.
In the present invention, graphene oxide solution is preferably prepared in accordance with the following methods: graphene oxide is dissolved in the water,
Ultrasonic under room temperature obtain graphene oxide solution；Described supersonic frequency is preferably 20～60khz, more preferably 30～50khz, then
It is preferably 40khz；The described ultrasonic time is preferably 10～40min, more preferably 10～30min, further preferably for 15～
25min, most preferably 20min；Described water is preferably deionized water；The quality of graphene oxide in described graphene oxide solution
Concentration be preferably 0.05%～0.6%, more preferably 0.05%～0.5%, further preferably for 0.05%～0.2%, further preferably for
0.05%～0.1%, most preferably 0.06%～0.08%；In some embodiments that the present invention provides, described graphite oxide
In alkene solution, the mass concentration of graphene oxide is preferably 0.075%.
Graphene oxide solution is mixed with ferrous salt solution；Ferrous salt in described ferrous salt solution is art technology
Water-soluble ferrous salt known to personnel, has no special restriction, is preferably ferrous chloride in the present invention；Described ferrous iron
In saline solution, the concentration of ferrous salt is preferably 0.1～0.6mol/l, more preferably 0.2～0.4mol/l, further preferably for 0.2～
0.3mol/l, most preferably 0.25mol/l；When ferrous salt solution is mixed with graphene oxide solution, preferably according to graphite oxide
In the quality of graphene oxide and ferrous salt solution in alkene solution, ferrous salt mass ratio is 1:(1～5) ratio mixing, more preferably
For 1:(2～4), further preferably for 1:(2.5～3.5), most preferably 1: 3；For making ferrous ion equably adsorb in graphite oxide
On alkene, described ferrous salt solution is preferably slowly added dropwise to graphene oxide solution；The rate of addition of described ferrous salt solution is excellent
Elect 0.1～1ml/s, more preferably 0.1～0.5ml/s as, further preferably for 0.2～0.4ml/s, most preferably 0.3ml/s；Deca
After finishing, mixing, obtain presoma mixed liquor.The method of described mixing is method well known to those skilled in the art, and
No special restriction, present invention preferably employs ultrasonic mixing；Described ultrasonic speed 20～60khz, more preferably 30～
50khz, further preferably for 40khz；The described ultrasonic time be preferably 10～60min, more preferably 20～40min, further preferably for
30～40min, most preferably 30min.
Add the first alkaline matter to adjust ph value in described presoma mixed liquor and be more than 8；Described first alkaline matter is
Alkaline matter well known to those skilled in the art, has no special restriction, in the present invention be preferably ammonia, sodium hydroxide with
One or more of potassium hydroxide, more preferably ammonia；The alkalescence of ammonia is little, discharges relatively slow after addition, so that arrive
Ferroferric oxide nano crystal is uniform；The concentration of described ammonia is preferably 0.5～2mol/l, more preferably 0.5～1.5mol/l,
It is further preferably 1mol/l；Described ammonia is preferably 1:(2～1 with the mol ratio of ferrous salt), more preferably 1:1；Described ammonia is excellent
Choosing is slowly added dropwise to presoma mixed liquor；The speed of described Deca is preferably 0.1～1ml/s, more preferably 0.1～0.5ml/
S, further preferably for 0.2～0.4ml/s, most preferably 0.3ml/s.
After adjusting ph value, reacted, obtained the first reactant liquor；Described reaction is carried out preferably under conditions of ultrasonic；Institute
State ultrasonic speed 20～60khz, more preferably 30～50khz, further preferably for 40khz；The temperature of described reaction is preferably 50
DEG C～70 DEG C, more preferably 55 DEG C～65 DEG C, further preferably for 60 DEG C；The time of described reaction is preferably 10～60min, more preferably
For 20～50min, further preferably for 20～40min, most preferably 30min.
Described first reactant liquor is mixed with pyrrolidones；Described pyrrolidones are this area skill
The compound containing pyrrolidone structure known to art personnel, has no special restriction, is preferably 2- pyrroles in the present invention
Alkanone and/or n- methyl pyrrolidone；Pyrrolidones can be received in established ferroso-ferric oxide as reaction monomers
The rice bonded active group of plane of crystal, and then under ammonium bromide class surfactant collective effect, promote ferriferrous oxide nano
Crystal grain self assembly is large-sized granule.Described pyrrolidones are preferred with the mass ratio of ferrous salt in ferrous salt solution
For 1:(1～10), more preferably 1:(3～10), further preferably for 1:(3～8) and, further preferably for 1:(5～7), most preferably 1: 6；
In the present invention, described pyrrolidones are added preferably in the form of pyrrolidones solution；Described pyrroles
The concentration of alkanone class compound solution be preferably 0.01～0.1mol/l, more preferably 0.02～0.08mol/l, further preferably for
0.03～0.07mol/l, further preferably for 0.04～0.06mol/l, most preferably 0.05mol/l；Described pyrrolidinone compounds chemical combination
Thing solution is preferably slowly added dropwise to the first reactant liquor；The speed of described pyrrolidones solution Deca is preferably 0.1
～1ml/s, more preferably 0.1～0.5ml/s, further preferably for 0.2～0.4ml/s, most preferably 0.3ml/s；After completion of dropping,
Mixing, the method for described mixing is preferably ultrasonic mixing；Described ultrasonic speed preferably 20～60khz, more preferably 30～
50khz, further preferably for 40khz.
After mixing, reaction, obtain the second reactant liquor；The temperature of described reaction is preferably 75 DEG C～95 DEG C, and more preferably 80
DEG C～95 DEG C, further preferably for 85 DEG C～95 DEG C, most preferably 90 DEG C；The time of described reaction is preferably 10～60min, more preferably
For 20～50min, further preferably for 20～40min, most preferably 30min.
Add the second alkaline matter to adjust its ph value in described second reactant liquor and be more than 11；Described second alkaline matter is
Alkaline matter well known to those skilled in the art, has no special restriction, in the present invention be preferably ammonia, sodium hydroxide with
One or more of potassium hydroxide, more preferably ammonia and sodium hydroxide；The concentration of described ammonia is same as above, and here is no longer
Repeat；Described ammonia is preferably 1:(1～3 with the mol ratio of sodium hydroxide), more preferably 1:(1～2), more preferably 1: 1；Institute
State the second alkaline matter to be preferably slowly added dropwise to the second reactant liquor；The rate of addition of described second alkaline matter be preferably 0.1～
1ml/s, more preferably 0.1～0.5ml/s, further preferably for 0.2～0.4ml/s, most preferably 0.3ml/s.
After adjusting the ph value of the second reactant liquor, reacted, obtained the 3rd reactant liquor；The temperature of described reaction is preferably 75
DEG C～95 DEG C, more preferably 80 DEG C～95 DEG C, further preferably for 85 DEG C～95 DEG C, most preferably 90 DEG C；Then not big less than 75 DEG C
Grain formation；The time of described reaction is preferably 10～60min, more preferably 20～50min, further preferably for 20～40min,
It is preferably 30min.
3rd reactant liquor is mixed with ammonium bromide class surfactant；Described ammonium bromide class surfactant is this area skill
The surfactant containing ammonium bromide structure known to art personnel, has no special restriction, is preferably 16 in the present invention
One or more of alkyl trimethyl ammonium bromide, Dodecyl trimethyl ammonium chloride and benzyl triethyl ammonium bromide；Described bromine
The addition changing ammonium class surfactant is to make it be preferably 1:(1～5 with the mol ratio of pyrrolidones), more preferably
For 1:(1～4), further preferably for 1:(1～3), most preferably 1: 2；Described ammonium bromide class surfactant is preferably with ammonium bromide class
Surfactant solution adds；The concentration of described ammonium bromide class surfactant solution is preferably 0.01～0.05mol/l, more excellent
Elect 0.01～0.04mol/l as, further preferably for 0.02～0.03mol/l, most preferably 0.02mol/l；Described ammonium bromide class table
Face activator solution is preferably slowly added dropwise to the 3rd reactant liquor；The speed of described ammonium bromide class surfactant solution Deca is excellent
Elect 0.1～1ml/s, more preferably 0.1～0.5ml/s as, further preferably for 0.2～0.4ml/s, most preferably 0.3ml/s；3rd
The method that reactant liquor is mixed with ammonium bromide class surfactant is preferably ultrasonic；Described ultrasonic frequency is preferably 20～60khz,
More preferably 30～50khz, further preferably for 40khz.
After mixing, reacted；The temperature of described reaction is preferably 75 DEG C～95 DEG C, more preferably 80 DEG C～95 DEG C, then
It is preferably 85 DEG C～95 DEG C, most preferably 90 DEG C；The time of described reaction preferably 100～400min, more preferably 160～
300min, further preferably for 180～300min, most preferably 180min.
After reaction, preferably by after black precipitate Magneto separate, washed respectively with alcoholic solvent with ultra-pure water, after lyophilization, obtain
To graphite oxide thiazolinyl ferriferrous oxide nano composite；Described alcoholic solvent for alcoholic solvent well known to those skilled in the art is
Can, have no special restriction, in the present invention, be preferably ethanol；The number of times of described washing preferably 2～4 times, more preferably 3 times.
According to the present invention, during preparing graphite oxide thiazolinyl ferriferrous oxide nano composite, preferably last for
Carry out ultrasonic；Described ultrasonic frequency is preferably 20～60khz, more preferably 30～50khz, further preferably for 40khz；Described step
Rapid s3), step s4) with step s5) be preferably sustained response, that is, in the middle of do not adjust temperature；In the present invention, all of solution is such as
No specified otherwise, is aqueous solution, preferably deionized water solution.
The present invention prepares the nucleus of graphite oxide thiazolinyl ferroso-ferric oxide by liquid-phase precipitation method, is subsequently adding surface activity
Agent growth in situ crystal, prepares graphite oxide thiazolinyl ferriferrous oxide nano composite under the conditions of low-temperature atmosphere-pressure, system
Without high temperature and high pressure environment during standby, effectively reduce energy loss and cost, without solvent commutation, effectively reduce technique step
And improve the dispersibility of composite suddenly,；And, ferroso-ferric oxide grows on graphene oxide two sides, in obvious copolymerization
Aggregate structure, so that graphene oxide is good with ferroso-ferric oxide associativity, does not reunite between graphene oxide layer, and then makes
Graphite oxide thiazolinyl ferriferrous oxide nano composite has excellent absorbing property.
The solvent-thermal method of abandoning tradition of the present invention prepares stone graphite oxide thiazolinyl ferriferrous oxide nano composite, adopts
Heating in water bath mode, prepares the graphite oxide thiazolinyl ferriferrous oxide nano composite of similar structures under low-temperature atmosphere-pressure, has
Effect reduces energy consumption needed for reaction system, it is to avoid change the complex process of solvent, improves the repeatability of composite, is a kind of new
The method preparing graphite oxide thiazolinyl ferriferrous oxide nano composite.
The present invention adopts two-step synthetic method, first adopts in situ synthesis to grow ferroso-ferric oxide in surface of graphene oxide
Nucleus, then under Action of Surfactant, ferroso-ferric oxide crystal grain is self-assembled into as bulky grain, and size reaches 200nm, and real
Existing graphenic surface is uniformly distributed, and utilizes the sterically hindered effect of ferriferrous oxide particles simultaneously, effectively stops graphene oxide
Lamella is reunited.
In preparation process of the present invention, do not use the high pollution reducing agent such as hydrazine hydrate, it is to avoid the poison to human body and environment
Property harm, reach nonhazardouss operating procedure, have the advantages that environment friendly and pollution-free.
In graphite oxide thiazolinyl ferriferrous oxide nano composite prepared by the present invention, ferroso-ferric oxide crystal grain self assembly
For ferroso-ferric oxide bulky grain uniform load on the surface of graphene oxide, the higher dielectric loss performance of graphene oxide and
The higher magnetic loss performance of ferroso-ferric oxide bulky grain, realizes the impedance matching of composite, makes electromagnetic wave penetrate composite
In delay being directed through of electromagnetic wave because the space steric effect of composite construction can hinder, realize high-selenium corn to electromagnetic wave.
Meanwhile, adjust the additional proportion of raw material divalent iron salt, the electromagnetic absorption frequency range of its composite can shift therewith, therefore may be used
To realize effective absorption of different electromagnetic bands.
Present invention also offers a kind of graphite oxide thiazolinyl ferriferrous oxide nano composite of said method preparation, institute
State ferriferrous oxide nano-particle and be assembled into ferroso-ferric oxide bulky grain, and be carried on the two sides of described graphene oxide；Described
The oarse-grained particle diameter of ferroso-ferric oxide is preferably 200～300nm.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described the enforcement it is clear that described
Example is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of not making creative work, broadly falls into the model of present invention protection
Enclose.
Embodiment 1
The graphene oxide solution of hummers method preparation is dissolved in deionized water (mass fraction is 1 ‰), often by 1.1
Ultrasonic and stir 20min and obtain graphene oxide dispersion soln under temperature.
The graphene oxide dispersion soln obtaining in 1.2 to 1.1 is slowly added dropwise 100ml solution of ferrous chloride (0.25mol/
L), continual ultrasonic stir 30min, obtains presoma mixed liquor.
The presoma mixed liquor obtaining in 1.3 to 1.2 is slowly added dropwise the 2% of 50ml ammonia spirit, and drop rate is
It is ensured that ph value ＞ 8, continual ultrasonic simultaneously stirs 30min to 0.3ml/s, and reaction temperature is 60 DEG C, obtains the first reactant liquor.
It is slowly added dropwise the 2-Pyrrolidone solution (0.05mol/l) of 50ml in 1.4 the first reactant liquors obtaining in 1.3,
Drop rate is 0.3ml/s, and continual ultrasonic simultaneously stirs 30min, and reaction temperature is 90 DEG C, obtains the second reactant liquor.
It is slowly added dropwise ammonia/sodium hydroxide mixed solution, drop rate is in 1.5 the second reactant liquors obtaining in 1.4
It is ensured that ph value ＞ 11, sodium hydroxide is 2:1 with the mol ratio of ammonia to 0.3ml/s, and continual ultrasonic simultaneously stirs 30min, reaction temperature
For 90 DEG C, obtain the 3rd reactant liquor.
It is slowly added dropwise the cetyl trimethylammonium bromide solution of 20ml in 1.6 the 3rd reactant liquors obtaining in 1.5
(0.02mol/l), drop rate is 0.3ml/s, continual ultrasonic stirring reaction 180min, obtains black precipitate after standing.
1.7 by the black precipitate obtaining in 1.6 Magneto separate, ultra-pure water and ethanol wash 3 times respectively after lyophilization, obtain
Graphite oxide thiazolinyl ferriferrous oxide nano composite.
The preparation flow schematic diagram of embodiment 1 is as shown in Figure 1.
Using x-ray diffraction, the graphite oxide thiazolinyl ferriferrous oxide nano composite obtaining in embodiment 1 is carried out
Analysis, obtains its x-ray diffraction spectrogram, as shown in Figure 2.As shown in Figure 2, the present embodiment has successfully prepared graphene oxide
Base ferriferrous oxide nano composite.
Using scanning electron microscope to the graphite oxide thiazolinyl ferriferrous oxide nano composite obtaining in embodiment 1
It is analyzed, obtain its stereoscan photograph, as shown in Figure 3.From the figure 3, it may be seen that ferroferric oxide nano granules self assembly balling-up
Shape structure is simultaneously uniformly supported on the surface of graphene oxide, and Fig. 2 illustration b is high magnification amplification picture, ferriferrous oxide nano
Particle size is in 200～300nm.
Using transmission electron microscope to the graphite oxide thiazolinyl ferriferrous oxide nano composite obtaining in embodiment 1
It is analyzed, obtain its transmission electron microscope photo, as shown in Figure 4.As shown in Figure 4, graphene oxide layer is sprawled as plane, four oxygen
Change three iron nano-particles and be evenly distributed on upper and lower surface, form class " Durio Zibethinus murr surface " structure, Fig. 4 illustration b is high magnification enlarged drawing
Piece is it is known that ferriferrous oxide particles part is hollow structure.
The powdered product graphite oxide thiazolinyl ferriferrous oxide nano composite that obtain the present embodiment and hard paraffin
4:6 uniformly mixes in mass ratio, using special die be compressed into external diameter 7.0mm, internal diameter 3.0mm, thickness 3.0mm coaxial
Style, tests its performance with model agilent te5071c vector network analyzer, and test frequency is 2～18ghz, obtains
Its absorbing property is as shown in figure 5, reaching absorption maximum in 7.05ghz is -26.3db, in 5.6～9.4ghz frequency range interior suction ripple
Reach below -10db, effectively absorbing width is 3.8ghz.
Embodiment 2
The graphene oxide solution of hummers method preparation is dissolved in deionized water (mass fraction is 1 ‰), often by 2.1
Ultrasonic and stir 20min and obtain graphene oxide dispersion soln under temperature.
It is slowly added dropwise 100ml copperas solution in the graphene oxide dispersion soln obtaining in 2.2 to 2.1
(0.25mol/l), drop rate is 0.3ml/s, and continual ultrasonic simultaneously stirs 30min, obtains presoma mixed liquor.
The presoma mixed liquor obtaining in 2.3 to 2.2 is slowly added dropwise the 2% of 50ml ammonia spirit, and drop rate is
It is ensured that ph value ＞ 8, continual ultrasonic simultaneously stirs 30min to 0.3ml/s, and reaction temperature is 60 DEG C, obtains the first reactant liquor；
It is slowly added dropwise the 2-Pyrrolidone solution (0.05mol/l) of 50ml in 2.4 the first reactant liquors obtaining in 2.3,
Drop rate is 0.3ml/s, and continual ultrasonic simultaneously stirs 30min, and reaction temperature is 90 DEG C, obtains the second reactant liquor.
It is slowly added dropwise ammonia/sodium hydroxide solution, drop rate is in 2.5 the second reactant liquors obtaining in 2.4
It is ensured that ph value ＞ 11, sodium hydroxide is 1:1 with the mol ratio of ammonia to 0.3ml/s, and continual ultrasonic simultaneously stirs 30min, reaction temperature
For 90 DEG C, obtain the 3rd reactant liquor.
It is slowly added dropwise the cetyl trimethylammonium bromide solution of 20ml in 2.6 the 3rd reactant liquors obtaining in 2.5
(0.02mol/l), drop rate is 0.3ml/s, continual ultrasonic stirring reaction 180min, obtains black precipitate after standing.
2.7 by the black precipitate obtaining in 2.6 Magneto separate, ultra-pure water and ethanol wash 3 times respectively after lyophilization, obtain
Graphite oxide thiazolinyl ferriferrous oxide nano composite.
Using x-ray diffraction, the graphite oxide thiazolinyl ferriferrous oxide nano composite obtaining in embodiment 2 is carried out
Analysis, obtains its x-ray diffraction spectrogram, as shown in Figure 2.As shown in Figure 2, the present embodiment is successfully prepared graphite oxide thiazolinyl four
Fe 3 O nano composite material.
The powdered product graphite oxide thiazolinyl ferriferrous oxide nano composite that prepare the present embodiment and solid
Paraffin 4:6 in mass ratio uniformly mixes, and is compressed into coaxial style using special die, and tests its absorbing property (method
With embodiment 1).As shown in figure 5, reaching maximum in 9.8ghz, its absorption maximum is -20.4db to its absorbing property, 8.6～
11.2ghz frequency range interior suction ripple reaches below -10db, and effectively absorbing width is 2.6ghz.
Embodiment 3
The graphene oxide solution of hummers method preparation is dissolved in deionized water (mass fraction is 1 ‰), often by 3.1
Ultrasonic and stir 20min and obtain graphene oxide dispersion soln under temperature.
The graphene oxide dispersion soln obtaining in 3.2 to 3.1 is slowly added dropwise 100ml solution of ferrous chloride (0.50mol/
L), drop rate is 0.3ml/s, and continual ultrasonic simultaneously stirs 30min, obtains presoma mixed liquor.
The presoma mixed liquor obtaining in 3.3 to 3.2 is slowly added dropwise the 2% of 50ml ammonia spirit, and drop rate is
It is ensured that ph value ＞ 8, continual ultrasonic simultaneously stirs 30min to 0.3ml/s, and reaction temperature is 60 DEG C, obtains the first reactant liquor.
It is slowly added dropwise the 2-Pyrrolidone solution (0.05mol/l) of 50ml in 3.4 the first reactant liquors obtaining in 3.3,
Drop rate is 0.3ml/s, and continual ultrasonic simultaneously stirs 30min, and reaction temperature is 90 DEG C, obtains the second reactant liquor.
It is slowly added dropwise ammonia/sodium hydroxide solution, drop rate is in 3.5 the second reactant liquors obtaining in 3.4
It is ensured that ph value ＞ 11, sodium hydroxide is 2:1 with the mol ratio of ammonia to 0.3ml/s, and continual ultrasonic simultaneously stirs 30min, reaction temperature
For 90 DEG C, obtain the 3rd reactant liquor.
It is slowly added dropwise the cetyl trimethylammonium bromide solution of 20ml in 3.6 the 3rd reactant liquors obtaining in 3.5
(0.02mol/l), drop rate is 0.3ml/s, continual ultrasonic stirring reaction 300min, obtains black precipitate after standing.
3.7 by the black precipitate obtaining in 3.6 Magneto separate, ultra-pure water and ethanol wash 3 times respectively after lyophilization, obtain
Graphite oxide thiazolinyl ferriferrous oxide nano composite.
Using x-ray diffraction, the graphite oxide thiazolinyl ferriferrous oxide nano composite obtaining in embodiment 3 is carried out
Analysis, obtains its x-ray diffraction spectrogram, as shown in Figure 2.As shown in Figure 2, the present embodiment has successfully prepared graphene oxide
Base ferriferrous oxide nano composite.
The powdered product preparing in embodiment 3 is uniformly mixed with hard paraffin 4:6 in mass ratio, using special mould
Tool is compressed into coaxial style, and tests its absorbing property (method is with embodiment 1).Its absorbing property as shown in figure 5,
Maximum is reached, its absorption maximum is -35.2db, reaches below -10db in 6.9～10.1ghz frequency range interior suction ripple, has during 8.4ghz
It is 3.2ghz that effect absorbs width.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that it is right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a kind of preparation method of graphite oxide thiazolinyl ferriferrous oxide nano composite is it is characterised in that include:
S1) graphene oxide solution is mixed with ferrous salt solution, obtain presoma mixed liquor；
S2) add the first alkaline matter to adjust ph value in described presoma mixed liquor and be more than 8, after reaction, obtain the first reaction
Liquid；
S3) described first reactant liquor is mixed with pyrrolidones, after reaction, obtain the second reactant liquor；
S4) add the second alkaline matter to adjust ph value in described second reactant liquor and be more than 11, after reaction, obtain the 3rd reaction
Liquid；
S5) described 3rd reactant liquor is mixed with ammonium bromide class surfactant, after reaction, obtain graphite oxide thiazolinyl four oxidation
Three-iron nano composite material.
2. preparation method according to claim 1 is it is characterised in that the mass concentration of described graphene oxide solution is
0.05%～0.6%；The molar concentration of described ferrous salt solution is 0.1～0.6mol/l.
3. preparation method according to claim 1 is it is characterised in that described pyrrolidones are 2-Pyrrolidone
And/or n- methyl pyrrolidone；Described ammonium bromide class surfactant is cetyl trimethylammonium bromide, dodecyl front three
One or more of base ammonium bromide and benzyl triethyl ammonium bromide.
4. preparation method according to claim 1 is it is characterised in that described pyrrolidones are with pyrrolidinone compounds
The form of compound solution is mixed with the first reactant liquor；Pyrrolidones in described pyrrolidones solution
Concentration is 0.01～0.1mol/l；
Described ammonium bromide class surfactant is mixed with the 3rd reactant liquor in the form of ammonium bromide class surfactant solution；Described
In ammonium bromide class surfactant solution, the concentration of ammonium bromide class surfactant is 0.01～0.05mol/l.
5. preparation method according to claim 4 is it is characterised in that described ferrous salt solution, pyrrolidones
Solution is each independently 0.1～0.5ml/s with the addition speed of ammonium bromide surfactant solution.
6. preparation method according to claim 1 is it is characterised in that graphene oxide in described graphene oxide solution
Mass ratio with the ferrous salt in ferrous salt solution is 1:(1～5)；
Described pyrrolidones are 1:(1～10 with the mass ratio of ferrous salt in ferrous salt solution)；Described ammonium bromide class
Surfactant is 1:(1～5 with the mol ratio of pyrrolidones).
7. preparation method according to claim 1 it is characterised in that
Described step s1) mix under ultrasound condition；The time of described mixing is 20～40min
Described step s2) reaction temperature be 50 DEG C～70 DEG C；The time of reaction is 20～40min；
Described step s3) in reaction temperature be 75 DEG C～95 DEG C；The time of reaction is 20～40min；
Described step s4) in reaction temperature be 75 DEG C～95 DEG C；The time of reaction is 20～40min；
Described step s5) in reaction temperature be 75 DEG C～95 DEG C；The time of reaction is 160～300min.
8. preparation method according to claim 1 is it is characterised in that described first alkaline matter is each with the second alkaline matter
From independently being one or more of ammonia, sodium hydroxide and potassium hydroxide.
9. preparation method according to claim 1 is it is characterised in that described second alkaline matter is ammonia and hydroxide
Sodium；Described sodium hydroxide is 1:(1～3 with the mol ratio of ammonia).
10. the graphite oxide thiazolinyl ferriferrous oxide nano composite prepared by a kind of claim 1～9 any one.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110145282A (en) * | 2019-06-03 | 2019-08-20 | 中国石油大学(华东) | A kind of method of loaded catalyst assisted microwave synthesis production of heavy oil reservoir |
| CN110317572A (en) * | 2018-03-29 | 2019-10-11 | 山东欧铂新材料有限公司 | Graphene oxide/ferriferrous oxide composite material method is prepared under a kind of normal pressure |
| CN110964480A (en) * | 2018-09-30 | 2020-04-07 | 山东欧铂新材料有限公司 | Graphene oxide/ferroferric oxide/zinc oxide composite material, preparation method thereof and graphene-based magnetic heat-conducting wave-absorbing material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533216A (en) * | 2011-12-27 | 2012-07-04 | 合肥希创电子科技有限公司 | Ferroferric oxide/reduced graphene oxide composite wave-absorbing material with hollow hemisphere structure and preparation method |
| CN103173189A (en) * | 2013-03-06 | 2013-06-26 | 西北工业大学 | Method for preparing reduced graphene oxide/ferroferric oxide nano-grade wave-absorbing materials |
| CN103418383A (en) * | 2013-08-23 | 2013-12-04 | 江苏科技大学 | Magnetic nanometer oxidized graphene and preparation method and application thereof |
| CN104479627A (en) * | 2015-01-12 | 2015-04-01 | 冯丹 | Nanometer wave-absorbing material |
| CN105289512A (en) * | 2015-12-01 | 2016-02-03 | 济南大学 | Oxalic acid-modified magnetic graphene oxide adsorbent for removing heavy metal ions and preparation method of adsorbent |
-
2016
- 2016-08-23 CN CN201610709758.1A patent/CN106334522B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533216A (en) * | 2011-12-27 | 2012-07-04 | 合肥希创电子科技有限公司 | Ferroferric oxide/reduced graphene oxide composite wave-absorbing material with hollow hemisphere structure and preparation method |
| CN103173189A (en) * | 2013-03-06 | 2013-06-26 | 西北工业大学 | Method for preparing reduced graphene oxide/ferroferric oxide nano-grade wave-absorbing materials |
| CN103418383A (en) * | 2013-08-23 | 2013-12-04 | 江苏科技大学 | Magnetic nanometer oxidized graphene and preparation method and application thereof |
| CN104479627A (en) * | 2015-01-12 | 2015-04-01 | 冯丹 | Nanometer wave-absorbing material |
| CN105289512A (en) * | 2015-12-01 | 2016-02-03 | 济南大学 | Oxalic acid-modified magnetic graphene oxide adsorbent for removing heavy metal ions and preparation method of adsorbent |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317572A (en) * | 2018-03-29 | 2019-10-11 | 山东欧铂新材料有限公司 | Graphene oxide/ferriferrous oxide composite material method is prepared under a kind of normal pressure |
| CN110317572B (en) * | 2018-03-29 | 2022-07-22 | 山东欧铂新材料有限公司 | Method for preparing graphene oxide/ferroferric oxide composite material under normal pressure |
| CN110964480A (en) * | 2018-09-30 | 2020-04-07 | 山东欧铂新材料有限公司 | Graphene oxide/ferroferric oxide/zinc oxide composite material, preparation method thereof and graphene-based magnetic heat-conducting wave-absorbing material |
| CN110145282A (en) * | 2019-06-03 | 2019-08-20 | 中国石油大学(华东) | A kind of method of loaded catalyst assisted microwave synthesis production of heavy oil reservoir |
| US11156069B2 (en) | 2019-06-03 | 2021-10-26 | China University Of Petroleum (East China) | Supported catalyst-assisted microwave method for exploiting heavy oil reservoir |
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