CN106334522B - A kind of graphite oxide alkenyl ferriferrous oxide nano composite material and preparation method - Google Patents
A kind of graphite oxide alkenyl ferriferrous oxide nano composite material and preparation method Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of graphite oxide alkenyl ferriferrous oxide nano composite material, comprising: S1) graphene oxide solution is mixed with ferrous salt solution, obtain presoma mixed liquor；S2 the first alkaline matter) is added in the presoma mixed liquor and adjusts pH value greater than 8, after reaction, obtains the first reaction solution；S3 first reaction solution is mixed with pyrrolidones), after reaction, obtains the second reaction solution；S4 the second alkaline matter) is added in second reaction solution and adjusts pH value greater than 11, after reaction, obtains third reaction solution；S5 the third reaction solution is mixed with ammonium bromide class surfactant), after reaction, obtains graphite oxide alkenyl ferriferrous oxide nano composite material.The present invention prepares the nucleus of ferroso-ferric oxide by liquid-phase precipitation method, and surfactant growth in situ crystal is then added, graphite oxide alkenyl ferriferrous oxide nano composite material is prepared under the conditions of low-temperature atmosphere-pressure.
Description
Technical field
The invention belongs to technical field of composite materials more particularly to a kind of graphite oxide alkenyl ferriferrous oxide nano are compound
Material and preparation method thereof.
Background technique
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 and electromagnetic interference problem generated in the electrical equipment course of work restricts people's production and life again, causes people
The further deterioration of class living environment.
Currently, electromagnetic wave becomes, one kind is novel to be had larger harmfulness and is not easy the pollution sources protected, it not only influences logical
News signal and seriously threaten the health of the mankind, and absorbing material due to can absorb project its surface electromagnetic wave energy thus
It is developed.Meanwhile absorbing material also has a wide range of applications in military stealth technology, therefore, novel absorbing material needs
There is excellent electro-magnetic wave absorption ability in electromagnetic regime as wide as possible, at the same to have both thickness it is thin, absorb frequency range
Wide, light weight and the high characteristic of intensity.
Graphene is a kind of new carbon being made of single carbon atom close-packed arrays, with biggish specific surface
Long-pending, good electric heating conductive performance.Meanwhile graphene has very high dielectric constant, is easy to be polarized in external electromagnetic field
Generate 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 particle has very important influence to its electromagnetic performance.Since absorbing material has higher want to the impedance matching of material
It asks, i.e., the dielectric constant of composite material and magnetic conductivity want close.Therefore, it is the high dielectric constant for meeting graphene, prepares big ruler
Very little ferriferrous oxide particles become trend.Surface of graphene oxide is not reduced and there are a large amount of oxygen-containing groups, utilizes its table
Graphene oxide and ferroso-ferric oxide are combined by the oxygen-containing group in face as the target spot in conjunction with nano material, can make electricity
Magnetic wave is hindered to delay being directed through for electromagnetic wave, the high dielectric of graphene oxide by space steric effect after penetrating composite material
Loss and the high magnetic loss of ferroso-ferric oxide, so that composite material has excellent electromagnetic wave absorption performance.
Conventional solvents thermal method prepares graphene-based ferriferrous oxide nano composite material and needs water phase graphene going to second
In the high boiling solvents such as glycol, commutation process is cumbersome and cannot completely remove water, by the reaction process such as high temperature and pressure, operation
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 using improved Hummers method synthesis graphene oxide, by coprecipitation by ferroferric oxide nano granules by certain
On proportional load to graphene oxide layer, but seriously accumulation overlapping between the composite material graphene sheet layer of its preparation, dispersion
Property is bad, is unfavorable for the raising of Radar Absorbing Properties of Composites.
Summary of the invention
In view of this, technical problem to be solved by the present invention lies in provide a kind of graphite oxide alkenyl ferroso-ferric oxide to receive
Nano composite material and preparation method thereof, this method is simple and obtained graphite oxide alkenyl ferriferrous oxide nano composite material tool
There is preferable absorbing property.
The present invention provides a kind of preparation methods of graphite oxide alkenyl ferriferrous oxide nano composite material, comprising:
S1 graphene oxide solution is mixed with ferrous salt solution), obtains presoma mixed liquor；
S2 the first alkaline matter) is added in the presoma mixed liquor and adjusts pH value greater than 8, after reaction, obtains first
Reaction solution；
S3 first reaction solution is mixed with pyrrolidones), after reaction, obtains the second reaction solution；
S4 the second alkaline matter) is added in second reaction solution and adjusts pH value greater than 11, after reaction, it is anti-to obtain third
Answer liquid；
S5 the third reaction solution is mixed with ammonium bromide class surfactant), after reaction, obtains graphite oxide alkenyl four
Fe 3 O nanocomposite.
Preferably, the mass concentration of the graphene oxide solution is 0.05%~0.6%；The ferrous salt solution rubs
Your concentration is 0.1~0.6mol/L.
Preferably, the pyrrolidones are 2-Pyrrolidone and/or n- methyl pyrrolidone；The ammonium bromide
Class surfactant is in cetyl trimethylammonium bromide, dodecyl trimethyl ammonium bromide and benzyl triethyl ammonium bromide
It is one or more.
Preferably, the pyrrolidones are mixed with the first reaction solution in the form of pyrrolidones solution
It closes；The concentration of pyrrolidones is 0.01~0.1mol/L in the pyrrolidones solution；
The ammonium bromide class surfactant is mixed in the form of ammonium bromide class surfactant solution with third reaction solution；
The concentration of ammonium bromide class surfactant is 0.01~0.05mol/L in the ammonium bromide class surfactant solution.
Preferably, the ferrous salt solution, pyrrolidones solution add with ammonium bromide surfactant solution
Enter rate and is each independently 0.1~0.5ml/s.
Preferably, the mass ratio of the ferrous salt in the graphene oxide and ferrous salt solution in the graphene oxide solution
For 1:(1~5)；
The mass ratio of ferrous salt is 1:(1~10 in the pyrrolidones and ferrous salt solution)；The bromination
The molar ratio of ammonium class surfactant and pyrrolidones is 1:(1~5).
Preferably,
The step S1) it is mixed under ultrasound condition；The mixed time is 20~40min
The step S2) reaction temperature be 50 DEG C~70 DEG C；The time of reaction is 20~40min；
The step S3) in reaction temperature be 75 DEG C~95 DEG C；The time of reaction is 20~40min；
The step S4) in reaction temperature be 75 DEG C~95 DEG C；The time of reaction is 20~40min；
The step S5) in reaction temperature be 75 DEG C~95 DEG C；The time of reaction is 160~300min.
Preferably, first alkaline matter and the second alkaline matter are each independently ammonium hydroxide, sodium hydroxide and hydrogen-oxygen
Change one of potassium or a variety of.
Preferably, second alkaline matter is ammonium hydroxide and sodium hydroxide；The molar ratio of the sodium hydroxide and ammonium hydroxide is
1:(1~3).
The present invention also provides a kind of graphite oxide alkenyl ferriferrous oxide nano composite materials.
The present invention provides a kind of preparation methods of graphite oxide alkenyl ferriferrous oxide nano composite material, comprising: S1)
Graphene oxide solution is mixed with ferrous salt solution, obtains presoma mixed liquor；S2) add in the presoma mixed liquor
Enter the first alkaline matter and adjust pH value greater than 8, after reaction, obtains the first reaction solution；S3) by first reaction solution and pyrrolidines
Ketone compounds mixing, after reaction, obtains the second reaction solution；S4 the second alkaline matter tune) is added in second reaction solution
It saves pH value and is greater than 11, after reaction, obtain third reaction solution；S5) the third reaction solution and ammonium bromide class surfactant are mixed
It closes, after reaction, obtains graphite oxide alkenyl ferriferrous oxide nano composite material.Compared with prior art, the present invention passes through liquid
The phase precipitation method prepare the nucleus of graphite oxide alkenyl ferroso-ferric oxide, surfactant growth in situ crystal are then added, low
Graphite oxide alkenyl ferriferrous oxide nano composite material is prepared under the conditions of normal temperature and pressure, is not necessarily to high temperature and pressure in preparation process
Energy loss and cost is effectively reduced in environment, is not necessarily to solvent commutation, effectively reduces processing step, and improve composite material
Dispersibility；Also, ferroso-ferric oxide is grown on graphene oxide two sides, is in apparent coaggregant structure, to make to aoxidize
Graphene is good with ferroso-ferric oxide associativity, does not reunite between graphene oxide layer, and then aoxidizes graphite oxide alkenyl four
Three-iron nanocomposite has excellent absorbing property.
The absorbing property maximum of graphite oxide alkenyl ferriferrous oxide nano composite material prepared by the present invention wash it is rear it is reachable-
35.2dB。
Detailed description of the invention
Fig. 1 is the preparation flow signal of graphite oxide alkenyl ferriferrous oxide nano composite material in the embodiment of the present invention 1
Figure；
Fig. 2 is that the X of graphite oxide alkenyl ferriferrous oxide nano composite material obtained in the embodiment of the present invention 1~3 is penetrated
Line diffraction spectrogram；
Fig. 3 is the stereoscan photograph of graphite oxide alkenyl ferriferrous oxide nano composite material obtained in embodiment 1；
Fig. 4 is the transmission electricity of graphite oxide alkenyl ferriferrous oxide nano composite material obtained in the embodiment of the present invention 1
Mirror photo；
Fig. 5 is the suction wave of graphite oxide alkenyl ferriferrous oxide nano composite material obtained in the embodiment of the present invention 1~3
Performance chart.
Specific embodiment
The present invention provides a kind of preparation methods of graphite oxide alkenyl ferriferrous oxide nano composite material, comprising: S1)
Graphene oxide solution is mixed with ferrous salt solution, obtains presoma mixed liquor；S2) add in the presoma mixed liquor
Enter the first alkaline matter and adjust pH value greater than 8, after reaction, obtains the first reaction solution；S3) by first reaction solution and pyrrolidines
Ketone compounds mixing, after reaction, obtains the second reaction solution；S4 the second alkaline matter tune) is added in second reaction solution
It saves pH value and is greater than 11, after reaction, obtain third reaction solution；S5) the third reaction solution and ammonium bromide class surfactant are mixed
It closes, after reaction, obtains graphite oxide alkenyl ferriferrous oxide nano composite material.
Wherein, the present invention is not particularly limited the source of all raw materials, can be self-control be also commercially available.
In the present invention, graphene oxide solution is preferably prepared in accordance with the following methods: graphene oxide is dissolved in the water,
Ultrasound obtains graphene oxide solution under room temperature；The supersonic frequency is preferably 20~60KHz, more preferably 30~50KHz, then
Preferably 40KHz；The time of the ultrasound is preferably 10~40min, more preferably 10~30min, further preferably for 15~
25min, most preferably 20min；The water is preferably deionized water；The quality of graphene oxide in the graphene oxide solution
Concentration is preferably 0.05%~0.6%, more preferably 0.05%~0.5%, be further preferably 0.05%~0.2%, further preferably for
0.05%~0.1%, most preferably 0.06%~0.08%；In some embodiments provided by the invention, the graphite oxide
The mass concentration of graphene oxide is preferably 0.075% in alkene solution.
Graphene oxide solution is mixed with ferrous salt solution；Ferrous salt in the ferrous salt solution is art technology
Water-soluble ferrous salt known to personnel has no special limitation, is preferably frerrous chloride in the present invention；The ferrous iron
The concentration of ferrous salt is preferably 0.1~0.6mol/L in salting liquid, 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
Ferrous salt mass ratio is 1:(1~5 in the quality of graphene oxide and ferrous salt solution in alkene solution) ratio mix, more preferably
For 1:(2~4), be further preferably 1:(2.5~3.5), most preferably 1: 3；To make ferrous ion equably be adsorbed on graphite oxide
On alkene, the ferrous salt solution is preferably slowly added dropwise into graphene oxide solution；The rate of addition of the ferrous salt solution is excellent
It is selected as 0.1~1ml/s, more preferably 0.1~0.5ml/s, is further preferably 0.2~0.4 ml/s, most preferably 0.3ml/s；Drop
After adding, mixing obtains presoma mixed liquor.The mixed method is method well known to those skilled in the art,
Special limitation is had no, present invention preferably employs ultrasonic mixings；20~60KHz of rate of the ultrasound, more preferably 30~
50KHz is further preferably 40KHz；The time of the ultrasound is preferably 10~60min, more preferably 20~40min, further preferably for
30~40min, most preferably 30min.
The first alkaline matter is added in the presoma mixed liquor and adjusts pH value greater than 8；First alkaline matter is
Alkaline matter well known to those skilled in the art, has no special limitation, in the present invention preferably ammonium hydroxide, sodium hydroxide with
One of potassium hydroxide is a variety of, more preferably ammonium hydroxide；The alkalinity of ammonium hydroxide is small, discharges relatively slowly, can make after addition
Ferroferric oxide nano crystal is uniform；The concentration of the ammonium hydroxide is preferably 0.5~2mol/L, more preferably 0.5~1.5mol/L,
It is further preferably 1mol/L；The molar ratio of the ammonium hydroxide and ferrous salt is preferably 1:(2~1), more preferably 1:1；The ammonium hydroxide is excellent
Choosing is slowly added dropwise into presoma mixed liquor；The speed of the dropwise addition is preferably 0.1~1ml/s, more preferably 0.1~
0.5ml/s is further preferably 0.2~0.4ml/s, most preferably 0.3ml/s.
After adjusting pH value, is reacted, obtain the first reaction solution；The reaction preferably carries out under conditions of ultrasound；Institute
20~60KHz of rate, the more preferably 30~50KHz for stating ultrasound, are further preferably 40KHz；The temperature of the reaction is preferably 50
DEG C~70 DEG C, more preferably 55 DEG C~65 DEG C, be further preferably 60 DEG C；The time of the reaction is preferably 10~60min, more preferably
It is further preferably 20~40min for 20~50min, most preferably 30min.
First reaction solution is mixed with pyrrolidones；The pyrrolidones are this field skill
Compound containing pyrrolidone structure known to art personnel has no special limitation, is preferably 2- pyrroles in the present invention
Alkanone and/or n- methyl pyrrolidone；Pyrrolidones can be used as reaction monomers, receive in established ferroso-ferric oxide
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 particle.The mass ratio of the pyrrolidones and ferrous salt in ferrous salt solution is preferred
For 1:(1~10), more preferably 1:(3~10), it is further preferably 1:(3~8) and, it is further preferably 1:(5~7), most preferably 1: 6；
In the present invention, the pyrrolidones are added preferably in the form of pyrrolidones solution；The pyrroles
The concentration of alkanone class compound solution is preferably 0.01~0.1mol/L, more preferably 0.02~0.08mol/L, further preferably for
0.03~0.07mol/L is further preferably 0.04~0.06mol/L, most preferably 0.05mol/L；The pyrrolidinone compounds chemical combination
Object solution is preferably slowly added dropwise into the first reaction solution；The speed that the pyrrolidones solution is added dropwise is preferably 0.1
~1ml/s, more preferably 0.1~0.5ml/s are further preferably 0.2~0.4ml/s, most preferably 0.3ml/s；It is added dropwise
Afterwards, it mixes, the mixed method is preferably ultrasonic mixing；The rate of the ultrasound is preferably 20~60KHz, and more preferably 30
~50KHz is further preferably 40KHz.
After mixing, reaction obtains the second reaction solution；The temperature of the reaction is preferably 75 DEG C~95 DEG C, more preferably 80
DEG C~95 DEG C, it is further preferably 85 DEG C~95 DEG C, most preferably 90 DEG C；The time of the reaction is preferably 10~60min, more preferably
It is further preferably 20~40min for 20~50min, most preferably 30min.
The second alkaline matter is added in second reaction solution and adjusts its pH value greater than 11；Second alkaline matter is
Alkaline matter well known to those skilled in the art, has no special limitation, in the present invention preferably ammonium hydroxide, sodium hydroxide with
One of potassium hydroxide is a variety of, more preferably ammonium hydroxide and sodium hydroxide；The concentration of the ammonium hydroxide is same as above, herein no longer
It repeats；The molar ratio of the ammonium hydroxide and sodium hydroxide is preferably 1:(1~3), more preferably 1:(1~2), more preferably 1: 1；Institute
The second alkaline matter is stated preferably to be slowly added dropwise to the second reaction solution；The rate of addition of second alkaline matter is preferably 0.1~
1ml/s, more preferably 0.1~0.5ml/s are further preferably 0.2~0.4ml/s, most preferably 0.3ml/s.
It after the pH value for adjusting the second reaction solution, is reacted, obtains third reaction solution；The temperature of the reaction is preferably 75
DEG C~95 DEG C, more preferably 80 DEG C~95 DEG C, be further preferably 85 DEG C~95 DEG C, most preferably 90 DEG C；Lower than 75 DEG C then without big
Crystal grain is formed；The time of the reaction is preferably 10~60min, more preferably 20~50min, is further preferably 20~40min, most
Preferably 30min.
Third reaction solution is mixed with ammonium bromide class surfactant；The ammonium bromide class surfactant is this field skill
Surfactant containing ammonium bromide structure known to art personnel has no special limitation, is preferably 16 in the present invention
One of alkyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide and benzyl triethyl ammonium bromide are a variety of；The bromine
The additional amount for changing ammonium class surfactant is that the molar ratio of itself and pyrrolidones is made to be preferably 1:(1~5), more preferably
For 1:(1~4), be further preferably 1:(1~3), most preferably 1: 2；The ammonium bromide class surfactant is preferably with ammonium bromide class
Surfactant solution is added；The concentration of the ammonium bromide class surfactant solution is preferably 0.01~0.05 mol/L, more
Preferably 0.01~0.04mol/L is further preferably 0.02~0.03mol/L, most preferably 0.02 mol/L；The ammonium bromide class
Surfactant solution is preferably slowly added dropwise into third reaction solution；The speed that the ammonium bromide class surfactant solution is added dropwise
Preferably 0.1~1ml/s, more preferably 0.1~0.5ml/s are further preferably 0.2~0.4ml/s, most preferably 0.3ml/s；The
The method that three reaction solutions are mixed with ammonium bromide class surfactant is preferably ultrasound；The frequency of the ultrasound is preferably 20~
60KHz, more preferably 30~50 KHz are further preferably 40KHz.
After mixing, reacted；The temperature of the reaction is preferably 75 DEG C~95 DEG C, and more preferably 80 DEG C~95 DEG C, then
Preferably 85 DEG C~95 DEG C, most preferably 90 DEG C；The time of the reaction is preferably 100~400 min, more preferably 160~
300min is further preferably 180~300min, most preferably 180min.
After reaction, preferably by after black precipitate Magneto separate, is washed with ultrapure water with alcoholic solvent, after freeze-drying, obtained respectively
To graphite oxide alkenyl ferriferrous oxide nano composite material；The alcoholic solvent is that alcoholic solvent well known to those skilled in the art is
Can, special limitation is had no, is preferably ethyl alcohol in the present invention；The number of the washing is preferably 2~4 times, and more preferably 3 times.
It is preferably lasted for during preparing graphite oxide alkenyl ferriferrous oxide nano composite material according to the present invention
Carry out ultrasound；The frequency of the ultrasound is preferably 20~60KHz, more preferably 30~50KHz, is further preferably 40KHz；The step
Rapid S3), step S4) with step S5) be preferably sustained response, i.e., it is intermediate without adjustment temperature；All solution is such as in the present invention
It is aqueous solution without specified otherwise, preferably deionized water solution.
The present invention prepares the nucleus of graphite oxide alkenyl ferroso-ferric oxide by liquid-phase precipitation method, and surface-active is then added
Graphite oxide alkenyl ferriferrous oxide nano composite material is prepared in agent growth in situ crystal under the conditions of low-temperature atmosphere-pressure, system
It is not necessarily to high temperature and high pressure environment during standby, energy loss and cost is effectively reduced, is not necessarily to solvent commutation, effectively reduces technique step
Suddenly, and the dispersibility of composite material is improved；Also, ferroso-ferric oxide is grown on graphene oxide two sides, in apparent copolymerization
Aggregate structure is not reunited, and then make to keep graphene oxide good with ferroso-ferric oxide associativity between graphene oxide layer
Graphite oxide alkenyl ferriferrous oxide nano composite material has excellent absorbing property.
The solvent-thermal method of abandoning tradition of the present invention prepares stone graphite oxide alkenyl ferriferrous oxide nano composite material, uses
Heating water bath mode prepares the graphite oxide alkenyl ferriferrous oxide nano composite material of similar structures under low-temperature atmosphere-pressure, has
Energy consumption needed for effect reduces reaction system, avoids the complex process for changing solvent, improves the repeatability of composite material, is a kind of novel
The method for preparing graphite oxide alkenyl ferriferrous oxide nano composite material.
The present invention uses two-step synthetic method, first grows ferroso-ferric oxide in surface of graphene oxide using in situ synthesis
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 graphene surface is uniformly distributed, while being acted on using the steric hindrance of ferriferrous oxide particles, effectively prevention graphene oxide
Lamella is reunited.
In preparation process of the present invention, without using high pollutions reducing agents such as hydrazine hydrates, the poison to human body and environment is avoided
Property harm, reach nonhazardous operating procedure, have the advantages that environment friendly and pollution-free.
In graphite oxide alkenyl ferriferrous oxide nano composite material prepared by the present invention, ferroso-ferric oxide crystal grain self assembly
For ferroso-ferric oxide bulky grain and uniform load is 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 material, electromagnetic wave is made to penetrate composite material
In can hinder to delay being directed through for electromagnetic wave due to the space steric effect of composite construction, realize the high-selenium corn to electromagnetic wave.
Meanwhile the additional proportion of raw material divalent iron salt is adjusted, the electromagnetic absorption frequency range of composite material can shift therewith, therefore can
To realize effective absorption of different electromagnetic bands.
The present invention also provides a kind of graphite oxide alkenyl ferriferrous oxide nano composite material of above method preparation, institutes
It states ferriferrous oxide nano-particle and is assembled into ferroso-ferric oxide bulky grain, and be carried on the two sides of the graphene oxide；It is described
The partial size of ferroso-ferric oxide bulky grain is preferably 200~300nm.
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
Graphene oxide solution prepared by Hummers method is dissolved in deionized water (mass fraction is 1 ‰) by 1.1, often
Temperature, which descends ultrasound and stirs 20min, obtains graphene oxide dispersion solution.
1.2 are slowly added dropwise 100ml solution of ferrous chloride (0.25mol/ to the dispersion solution of graphene oxide obtained in 1.1
L), continual ultrasonic and 30min is stirred, obtains presoma mixed liquor.
1.3 2% ammonia spirit of 50ml is slowly added dropwise to presoma mixed liquor obtained in 1.2, and drop rate is
0.3ml/s guarantees that pH value > 8, continual ultrasonic simultaneously stir 30min, and reaction temperature is 60 DEG C, obtains the first reaction solution.
The 2-Pyrrolidone solution (0.05 mol/L) of 50ml is slowly added dropwise in 1.4 first reaction solutions obtained 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 reaction solution.
Ammonium hydroxide/sodium hydroxide mixed solution is slowly added dropwise in 1.5 second reaction solutions obtained in 1.4, drop rate is
The molar ratio of 0.3ml/s, guarantee pH value > 11, sodium hydroxide and ammonium hydroxide is 2:1, and continual ultrasonic simultaneously stirs 30min, reaction temperature
It is 90 DEG C, obtains third reaction solution.
The cetyl trimethylammonium bromide solution of 20ml is slowly added dropwise in the 1.6 third reaction solutions obtained in 1.5
(0.02mol/L), drop rate 0.3ml/s, continual ultrasonic are simultaneously stirred to react 180min, obtain black precipitate after standing.
1.7 by black precipitate Magneto separate obtained in 1.6, and ultrapure water and ethyl alcohol are freeze-dried after washing 3 times respectively, obtains
Graphite oxide alkenyl ferriferrous oxide nano composite material.
The preparation flow schematic diagram of embodiment 1 is as shown in Figure 1.
Graphite oxide alkenyl ferriferrous oxide nano composite material obtained in embodiment 1 is carried out using X-ray diffraction
Analysis, obtains its X-ray diffraction spectrogram, as shown in Figure 2.As shown in Figure 2, graphene oxide has successfully been prepared in the present embodiment
Base ferriferrous oxide nano composite material.
Using scanning electron microscope to graphite oxide alkenyl ferriferrous oxide nano composite material obtained in embodiment 1
It is analyzed, obtains 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 and the surface for being uniformly supported on graphene oxide, Fig. 3 illustration B are high magnification amplification picture, ferriferrous oxide nano
Particle size is in 200~300nm or so.
Using transmission electron microscope to graphite oxide alkenyl ferriferrous oxide nano composite material obtained in embodiment 1
It is analyzed, obtains 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 " durian surface " structure, Fig. 4 illustration B is high magnification enlarged drawing
Piece, it is known that ferriferrous oxide particles part is hollow structure.
The powdered product graphite oxide alkenyl ferriferrous oxide nano composite material and solid paraffin that the present embodiment is obtained
4:6 is uniformly mixed in mass ratio, using special die be compressed into outer diameter 7.0mm, internal diameter 3.0mm, thickness 3.0mm it is same
Shaft type sample tests its performance with model Agilent TE5071C vector network analyzer, and test frequency is 2~18GHz, is obtained
To its absorbing property as shown in figure 5, reaching absorption maximum in 7.05 GHz is -26.3dB, in 5.6~9.4GHz frequency range interior suction
Wave reaches -10dB hereinafter, effectively absorbing width is 3.8GHz.
Embodiment 2
Graphene oxide solution prepared by Hummers method is dissolved in deionized water (mass fraction is 1 ‰) by 2.1, often
Temperature, which descends ultrasound and stirs 20min, obtains graphene oxide dispersion solution.
2.2 are slowly added dropwise 100ml ferrous sulfate solution into the dispersion solution of graphene oxide obtained in 2.1
(0.25mol/L), drop rate 0.3ml/s, continual ultrasonic simultaneously stir 30min, obtain presoma mixed liquor.
2.3 2% ammonia spirit of 50ml is slowly added dropwise to presoma mixed liquor obtained in 2.2, and drop rate is
0.3ml/s guarantees that pH value > 8, continual ultrasonic simultaneously stir 30min, and reaction temperature is 60 DEG C, obtains the first reaction solution；
The 2-Pyrrolidone solution (0.05 mol/L) of 50ml is slowly added dropwise in 2.4 first reaction solutions obtained 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 reaction solution.
Ammonium hydroxide/sodium hydroxide solution is slowly added dropwise in 2.5 second reaction solutions obtained in 2.4, drop rate is
The molar ratio of 0.3ml/s, guarantee pH value > 11, sodium hydroxide and ammonium hydroxide is 1:1, and continual ultrasonic simultaneously stirs 30min, reaction temperature
It is 90 DEG C, obtains third reaction solution.
The cetyl trimethylammonium bromide solution of 20ml is slowly added dropwise in the 2.6 third reaction solutions obtained in 2.5
(0.02mol/L), drop rate 0.3ml/s, continual ultrasonic are simultaneously stirred to react 180min, obtain black precipitate after standing.
2.7 by black precipitate Magneto separate obtained in 2.6, and ultrapure water and ethyl alcohol are freeze-dried after washing 3 times respectively, obtains
Graphite oxide alkenyl ferriferrous oxide nano composite material.
Graphite oxide alkenyl ferriferrous oxide nano composite material obtained in embodiment 2 is carried out using X-ray diffraction
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 alkenyl four
Fe 3 O nanocomposite.
The powdered product graphite oxide alkenyl ferriferrous oxide nano composite material and solid that the present embodiment is prepared
Paraffin 4:6 in mass ratio is uniformly mixed, and is compressed into coaxial style using special die, and tests its absorbing property (method
With embodiment 1).For its absorbing property as shown in figure 5, reaching maximum in 9.8GHz, absorption maximum is -20.4dB, 8.6~
11.2GHz frequency range interior suction wave reaches -10dB hereinafter, effectively absorbing width is 2.6GHz.
Embodiment 3
Graphene oxide solution prepared by Hummers method is dissolved in deionized water (mass fraction is 1 ‰) by 3.1, often
Temperature, which descends ultrasound and stirs 20min, obtains graphene oxide dispersion solution.
3.2 are slowly added dropwise 100ml solution of ferrous chloride (0.50mol/ to the dispersion solution of graphene oxide obtained in 3.1
L), drop rate 0.3ml/s, continual ultrasonic simultaneously stir 30min, obtain presoma mixed liquor.
3.3 2% ammonia spirit of 50ml is slowly added dropwise to presoma mixed liquor obtained in 3.2, and drop rate is
0.3ml/s guarantees that pH value > 8, continual ultrasonic simultaneously stir 30min, and reaction temperature is 60 DEG C, obtains the first reaction solution.
The 2-Pyrrolidone solution (0.05 mol/L) of 50ml is slowly added dropwise in 3.4 first reaction solutions obtained 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 reaction solution.
Ammonium hydroxide/sodium hydroxide solution is slowly added dropwise in 3.5 second reaction solutions obtained in 3.4, drop rate is
The molar ratio of 0.3ml/s, guarantee pH value > 11, sodium hydroxide and ammonium hydroxide is 2:1, and continual ultrasonic simultaneously stirs 30min, reaction temperature
It is 90 DEG C, obtains third reaction solution.
The cetyl trimethylammonium bromide solution of 20ml is slowly added dropwise in the 3.6 third reaction solutions obtained in 3.5
(0.02mol/L), drop rate 0.3ml/s, continual ultrasonic are simultaneously stirred to react 300min, obtain black precipitate after standing.
3.7 by black precipitate Magneto separate obtained in 3.6, and ultrapure water and ethyl alcohol are freeze-dried after washing 3 times respectively, obtains
Graphite oxide alkenyl ferriferrous oxide nano composite material.
Graphite oxide alkenyl ferriferrous oxide nano composite material obtained in embodiment 3 is carried out using X-ray diffraction
Analysis, obtains its X-ray diffraction spectrogram, as shown in Figure 2.As shown in Figure 2, graphene oxide has successfully been prepared in the present embodiment
Base ferriferrous oxide nano composite material.
The powdered product being prepared in embodiment 3 is uniformly mixed with solid paraffin 4:6 in mass ratio, utilizes 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,
Reach maximum when 8.4GHz, absorption maximum is -35.2dB, reach -10dB in 6.9~10.1GHz frequency range interior suction wave hereinafter,
Effectively absorbing width is 3.2GHz.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of preparation method of graphite oxide alkenyl ferriferrous oxide nano composite material characterized by comprising
S1 graphene oxide solution is mixed with ferrous salt solution), obtains presoma mixed liquor；
S2 the first alkaline matter) is added in the presoma mixed liquor and adjusts pH value greater than 8, after reaction, obtains the first reaction
Liquid；The step S2) reaction temperature be 50 DEG C~70 DEG C；The time of reaction is 20~40min；
S3 first reaction solution is mixed with pyrrolidones), after reaction, obtains the second reaction solution；The step
S3 the reaction temperature in) is 75 DEG C~95 DEG C；The time of reaction is 20~40min；
S4 the second alkaline matter) is added in second reaction solution and adjusts pH value greater than 11, after reaction, obtains third reaction
Liquid；The step S4) in reaction temperature be 75 DEG C~95 DEG C；The time of reaction is 20~40min；
S5 the third reaction solution is mixed with ammonium bromide class surfactant), after reaction, obtains the oxidation of graphite oxide alkenyl four
Three-iron nanocomposite；The step S5) in reaction temperature be 75 DEG C~95 DEG C；The time of reaction is 160~300min.
2. preparation method according to claim 1, which is characterized in that the mass concentration of the graphene oxide solution is
0.05%~0.6%；The molar concentration of the ferrous salt solution is 0.1~0.6mol/L.
3. preparation method according to claim 1, which is characterized in that the pyrrolidones are 2-Pyrrolidone
And/or n- methyl pyrrolidone；The ammonium bromide class surfactant is cetyl trimethylammonium bromide, dodecyl front three
One of base ammonium bromide and benzyl triethyl ammonium bromide are a variety of.
4. preparation method according to claim 1, which is characterized in that the pyrrolidones are with pyrrolidinone compounds
The form of compound solution is mixed with the first reaction solution；Pyrrolidones in the pyrrolidones solution
Concentration is 0.01~0.1mol/L；
The ammonium bromide class surfactant is mixed in the form of ammonium bromide class surfactant solution with third reaction solution；It is described
The concentration of ammonium bromide class surfactant is 0.01~0.05mol/L in ammonium bromide class surfactant solution.
5. the preparation method according to claim 4, which is characterized in that the ferrous salt solution, pyrrolidones
The addition rate of solution and ammonium bromide surfactant solution is each independently 0.1~0.5ml/s.
6. preparation method according to claim 1, which is characterized in that the graphene oxide in the graphene oxide solution
Mass ratio with the ferrous salt in ferrous salt solution is 1:(1~5)；
The mass ratio of ferrous salt is 1:(1~10 in the pyrrolidones and ferrous salt solution)；The ammonium bromide class
The molar ratio of surfactant and pyrrolidones is 1:(1~5).
7. preparation method according to claim 1, which is characterized in that
The step S1) it is mixed under ultrasound condition；The mixed time is 20~40min.
8. preparation method according to claim 1, which is characterized in that first alkaline matter and the second alkaline matter are each
From independently being one of ammonium hydroxide, sodium hydroxide and potassium hydroxide or a variety of.
9. preparation method according to claim 1, which is characterized in that second alkaline matter is ammonium hydroxide and hydroxide
Sodium；The molar ratio of the sodium hydroxide and ammonium hydroxide is 1:(1~3).
10. graphite oxide alkenyl ferriferrous oxide nano prepared by a kind of claim 1~9 any one preparation method is compound
Material.
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| 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 |
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| CN104479627A (en) * | 2015-01-12 | 2015-04-01 | 冯丹 | Nanometer wave-absorbing material |
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| 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 |
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