CN106118594B - A kind of preparation method of graphene oxide/ferriferrous oxide composite material - Google Patents
A kind of preparation method of graphene oxide/ferriferrous oxide composite material Download PDFInfo
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Abstract
It is especially a kind of with the different graphene oxide/ferriferrous oxide composite material preparation methods for inhaling wave frequency section the present invention provides a kind of preparation method of graphene oxide/ferriferrous oxide composite material.The present invention, by specific heating and ultrasonic step, in the case where not needing any reducing agent, has obtained graphene oxide/ferriferrous oxide composite material under conditions of only with heating and ultrasound；And composite material ferroferric oxide nano granules close-packed arrays prepared by the present invention but it is evenly dispersed, form class " file surface " structure, it also effectively solves the dispersion between graphene sheet layer, realizes ferroferric oxide nano granules on the surface of graphene evenly dispersed evenly dispersed between graphene sheet layer.Preparation method simple process provided by the invention, does not use any reducing agent catalyst at mild condition, does not introduce impurity, can effectively reduce the discharge of waste, safety and environmental protection is more suitable for scale industrial production.
Description
Technical field
The invention belongs to absorbing material technical fields, are related to a kind of system of graphene oxide/ferriferrous oxide composite material
Preparation Method more particularly to a kind of graphene oxide/ferroso-ferric oxide composite wave-suction material preparations with different suction wave frequency sections
Method.
Background technique
Electromagnetic pollution refers to the interference and harmful electromagnetic radiation of natural and artificial various electromagnetic waves.Due to broadcast, electricity
Depending on the development of, microwave technology, radio-frequency apparatus power is multiplied, and the electromagnetic radiation on ground increases considerably, and has reached directly
Threaten the degree of human health.The interaction variation of electric and magnetic fields generates electromagnetic wave.Electromagnetism wave direction air-launched or the flood that converges show
As crying electromagnetic radiation, excessive electromagnetic radiation has resulted in electromagnetic pollution.
With the rapid development of microwave and mechanics of communication, increasingly threat of the severe electromagnetic pollution to environment and bio-safety
Increasingly it is taken seriously.Harm caused by electromagnetic pollution can not be underestimated, and in Modern Family, electromagnetic wave is made for people
While good fortune, also with the effect of " electronic smoke ", directly or indirectly it is detrimental to health.The study found that electromagnetic radiation pair
Public's body has long-term potential threat and influences, and for a long time by electromagenetic wave radiation, human tissue organ can be by its long-term damage
Lesion can occur for accumulation；Electromagnetic radiation even also will cause catastrophic effect to the strong jamming of military installations, aviation.Therefore, newly
The absorbing material of type needs to have excellent electro-magnetic wave absorption ability in electromagnetic regime as wide as possible, while to have both thickness
Spend thin, light weight and the high characteristic of intensity.
Graphene is a kind of with bi-dimensional cellular shape nanostructure, the novel carbon materials being made of single carbon atom close-packed arrays
Material, with biggish specific surface area, good electric heating conductive performance.Meanwhile graphene has very high dielectric constant, in electricity
It can be polarized by external magnetic field in magnetic field, and electric dipole moves with electric field and relaxation occurs inside grapheme material, consumption part electricity
Can and make dielectric itself and generate heat, i.e. generation dielectric loss.Single graphene sheet layer is easily penetrated by electromagnetic wave and loses electromagnetism
Wave absorbability, meanwhile, single high dielectric loss also results in the difficulty of impedance matching.By the way that graphene and four are aoxidized three
Iron carry out it is compound, by barrier effect between quantum dot array and space steric effect after electromagnetic wave being made to penetrate composite material
Obstruction delays being directed through for electromagnetic wave, so that playing reduces wave frequency effect.Meanwhile four oxygen of graphene surface load
Changing three iron nano-particles can be by mechanism such as magnetic hystersis loss, eddy-current loss and ferromagnetic resonances come electromagnetic wave absorption.Thus, oxidation
Graphene/ferriferrous oxide composite material receives the extensive concern of scholar in field.
But existing graphene oxide/ferroso-ferric oxide composite wave-suction material preparation method is needed mostly using water
The noxious materials such as hydrazine are closed as reducing agent, not only processing step is complicated, but also the requirement to production equipment is also higher, it is difficult to realize
Large-scale production and application.In addition to this, the use of poisonous and harmful raw material there is also pollution environment and poisons the latent of human health
In risk.
Therefore, the preparation method for how finding a kind of more optimal graphene oxide/ferriferrous oxide composite material, makes
Process conditions are mild, safety and environmental protection, it has also become many manufacturers in the industry and line research staff major issue urgently to be resolved.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of graphene oxide with absorbing property/
The preparation method of ferriferrous oxide composite material, it is especially a kind of with the different graphene oxides for inhaling wave frequency section/tetra- oxidations three
The preparation method of iron composite wave-suction material, the preparation method of graphene oxide/ferriferrous oxide composite material provided by the invention
Simple process, mild condition, safety and environmental protection are suitble to large-scale industrial production, but also enable to ferriferrous oxide particles
Surface of graphene oxide it is evenly dispersed and have adjustable function, thus have preferable absorbing property and different suction wave frequencies
Section.
The present invention provides a kind of preparation methods of graphene oxide/ferriferrous oxide composite material, comprising the following steps:
A) by graphene oxide solution after ultrasonic disperse, graphene oxide dispersion is obtained；
B) graphene oxide dispersion for obtaining above-mentioned steps adds two by heating with after second of ultrasonic disperse
Valence source of iron, obtains precursor mixed solution；
C) precursor mixed solution that above-mentioned steps obtain is heated and is ultrasonically treated again, obtains semi-finished product；
D aqueous slkali) is added into the semi-finished product that above-mentioned steps obtain, after carrying out thermostatic ultrasonic processing, obtains graphite oxide
Alkene/ferriferrous oxide composite material.
Preferably, the concentration of the graphene oxide solution is 0.5~1.5mg/mL；
The divalent source of iron is ferrous salt solution；
The ferrous salt includes one of ferrous sulfate, frerrous chloride and ferrous nitrate or a variety of；
The concentration of the ferrous salt solution is 0.005~0.03mol/L.
Preferably, change the additional amount of the divalent source of iron, the graphene oxide/ferriferrous oxide composite material is tool
There are the different graphene oxide/ferriferrous oxide composite materials for inhaling wave frequency section.
Preferably, the step D) specifically: aqueous slkali is added into the semi-finished product that above-mentioned steps obtain, it is super to carry out constant temperature
After sonication, adds surfactant and carry out after being ultrasonically treated again, obtain graphene oxide/ferroso-ferric oxide composite wood
Material.
Preferably, the step B) in, the temperature of the heating is 30~70 DEG C；
The frequency of second of ultrasonic disperse is 20~60KHz, time of second of ultrasonic disperse is 10~
50min；
The step B) in, described to add to be slowly added dropwise, the speed being slowly added dropwise is 1~10mL/min.
Preferably, the step C) in, the temperature heated again is 75~100 DEG C, the time heated again
For 90~150min；
The frequency of the ultrasonic treatment is 20~60KHz, and the time of the ultrasonic treatment is 10~50min.
Preferably, the aqueous slkali includes ammonium hydroxide and/or sodium hydroxide；
The concentration of the aqueous slkali is 1~10mol/L.
Preferably, the temperature of the thermostatic ultrasonic processing is 75~100 DEG C；The frequency of thermostatic ultrasonic processing is 20~
The time of 60KHz, the thermostatic ultrasonic processing are 90~150min；
The temperature being ultrasonically treated again is 75~100 DEG C；The frequency being ultrasonically treated again is 20~60KHz,
The time being ultrasonically treated again is 90~150min.
It preferably, further include vacuum drying step after the ultrasonic treatment again；
The vacuum drying temperature is 40~80 DEG C, and the vacuum drying time is 4~12h.
The present invention also provides a kind of absorbing materials, including graphite oxide prepared by above-mentioned technical proposal any one
Alkene/ferriferrous oxide composite material.
The present invention provides a kind of preparation methods of graphene oxide/ferriferrous oxide composite material, include the following steps,
First by graphene oxide solution after ultrasonic disperse, graphene oxide dispersion is obtained；Then above-mentioned steps are obtained
Graphene oxide dispersion adds divalent source of iron, obtains precursor mixed solution by heating with after second of ultrasonic disperse；
The precursor mixed solution that above-mentioned steps obtain is heated and is ultrasonically treated again again, obtains semi-finished product；Finally to above-mentioned
Aqueous slkali is added in the semi-finished product that step obtains, after carrying out thermostatic ultrasonic processing, it is compound to obtain graphene oxide/ferroso-ferric oxide
Material.Compared with prior art, the present invention is under conditions of only with heating and ultrasound, by specific heating and ultrasonic step,
Under conditions of not needing any reducing agent, graphene oxide/ferriferrous oxide composite material has been obtained, it is often more important that, this
It invents the composite material ferroferric oxide nano granules close-packed arrays of preparation but evenly dispersed, forms class " file surface " knot
Structure, the dispersion between effective solution graphene sheet layer, realizes ferroferric oxide nano granules on the surface of graphene
It is evenly dispersed.The present invention fundamentally solves in existing preparation process, uses hydrazine hydrate, sodium borohydride or ascorbic acid
The defects of reducing agents such as sodium not only endanger environment and production operation health, but also there may be impurity residuals, while preparing
Composite structure is imperfect, and nano particle is mutually accumulated, and dispersion is uneven, and the absorbing property etc. for substantially reducing composite material is asked
Topic.Preparation method simple process provided by the invention, does not use any reducing agent catalyst at mild condition, does not introduce impurity, energy
The effective discharge for reducing waste, safety and environmental protection are more suitable for scale industrial production, have certain economic benefit and society
Benefit.The experimental results showed that ferroso-ferric oxide/graphene oxide composite material prepared by the present invention has excellent wave absorbtion
Can, and the suction wave frequency section of composite material shifts with the additional amount variation of divalent iron salt, realizes the electromagnetic wave of different frequency range
It absorbs.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of graphene oxide/ferriferrous oxide composite material prepared by the present invention；
Fig. 2 is graphene oxide/ferriferrous oxide composite material scanning electron microscope prepared by the embodiment of the present invention 1
Photo；
Fig. 3 is graphene oxide/ferriferrous oxide composite material transmission electron microscope prepared by the embodiment of the present invention 1
Photo；
Fig. 4 is the microwave reflection attenuation curve figure of absorbing material prepared by the present invention；
Fig. 5 is the transmission electron microscope picture of graphene oxide/ferriferrous oxide composite material prepared by the present invention；
Fig. 6 is the transmission electron microscope picture of graphene oxide/ferriferrous oxide composite material prepared by the present invention.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze in pure or field to use
Conventional purity.
The present invention provides a kind of preparation methods of graphene oxide/ferriferrous oxide composite material, comprising the following steps:
A) by graphene oxide solution after ultrasonic disperse, graphene oxide dispersion is obtained；
B) graphene oxide dispersion for obtaining above-mentioned steps adds two by heating with after second of ultrasonic disperse
Valence source of iron, obtains precursor mixed solution；
C) precursor mixed solution that above-mentioned steps obtain is heated and is ultrasonically treated again, obtains semi-finished product；
D aqueous slkali) is added into the semi-finished product that above-mentioned steps obtain, after carrying out thermostatic ultrasonic processing, obtains graphite oxide
Alkene/ferriferrous oxide composite material.
The present invention obtains graphene oxide dispersion first by graphene oxide solution after ultrasonic disperse.The present invention
The source of the graphene oxide solution is not particularly limited, with preparation method well known to those skilled in the art preparation or city
Sell purchase.The concentration of the graphene oxide solution is not particularly limited in the present invention, known to those skilled in the art
Graphene oxide solution normal concentration, the concentration of graphene oxide solution of the present invention is preferably 0.5~
1.5mg/mL, more preferably 0.6~1.4mg/mL, more preferably 0.7~1.3mg/mL, most preferably 0.9~1.1mg/mL.This
The condition of the ultrasonic disperse is not particularly limited in invention, and the condition with ultrasonic disperse well known to those skilled in the art is
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement.
The present invention then the graphene oxide dispersion that obtains above-mentioned steps through heating and second of ultrasonic disperse after,
Divalent source of iron is added, precursor mixed solution is obtained.
The divalent source of iron is not particularly limited in the present invention, with divalent source of iron well known to those skilled in the art,
Those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, and the present invention is excellent
It is selected as ferrous salt solution, includes more preferably one of ferrous sulfate, frerrous chloride and ferrous nitrate or a variety of, more preferably wraps
Include ferrous sulfate or frerrous chloride.The concentration of the ferrous salt solution is not particularly limited in the present invention, with those skilled in the art
The concentration of ferrous salt solution known to member, those skilled in the art can be according to practical condition, product requirement and matter
Amount requires to be selected and adjusted, and the concentration of ferrous salt solution of the present invention is preferably 0.005~0.03mol/L, more preferably
For 0.01~0.025mol/L, most preferably 0.015~0.02mol/L.
Using divalent source of iron, as raw material, the suction wave frequency section of composite material may be implemented with the addition of divalent source of iron in the present invention
Amount variation shifts, and by changing the divalent source of iron additional amount, realizes the electro-magnetic wave absorption of different frequency range；It is of the present invention
Inhale wave, that is, electromagnetic wave absorption；The specific suction wave frequency section is not particularly limited in the present invention, and those skilled in the art can root
According to practical condition, suction wave requires and quality requirement is selected and adjusted accordingly to the divalent source of iron additional amount.
The mode of the addition is not particularly limited in the present invention, and those skilled in the art can be according to actual production feelings
Condition, product requirement and quality requirement are selected and are adjusted, and the present invention is to improve ion reaction and ultrasonic cavitation effect, described
It adds and is preferably slowly added dropwise；The speed being slowly added dropwise is preferably 1~10mL/min, more preferably 2~9mL/min,
More preferably 3~8mL/min, most preferably 5~6mL/min.
The temperature of heating of the present invention is preferably 30~70 DEG C, more preferably 35~65 DEG C, more preferably 40~60 DEG C,
Most preferably 45~55 DEG C.The frequency of second of ultrasonic disperse of the present invention is preferably 20~60KHz, more preferably 25~
55KHz, more preferably 30~50KHz, most preferably 40KHz；The time of second of ultrasonic disperse is preferably 10~
50min, more preferably 15~45min, more preferably 20~40min, most preferably 25~35min.
The present invention carries out the ultrasound of specific frequency and time simultaneously within specified temperatures, helps to improve ion reaction
And ultrasonic cavitation effect.
The precursor mixed solution that above-mentioned steps obtain then is heated and is ultrasonically treated again by the present invention, obtains half
Finished product；
The temperature of the present invention heated again is preferably 75~100 DEG C, and more preferably 35~65 DEG C, more preferably 40~
60 DEG C, most preferably 45~55 DEG C；The time of the present invention heated again is preferably 90~150min, more preferably 100~
140min, more preferably 110~130min, most preferably 115~125min.
Ultrasonic treatment of the present invention preferably stirring ultrasonic treatment；The frequency of ultrasonic treatment of the present invention is preferably 20
~60KHz, more preferably 25~55KHz, more preferably 30~50KHz, most preferably 40KHz；The time of the ultrasonic treatment
Preferably 10~50min, more preferably 15~45min, more preferably 20~40min, most preferably 25~35min.
The present invention carries out the ultrasound of specific frequency and time within specified temperatures, forms gradient with temperature before and becomes
Change, while above-mentioned ultrasonic time is short, heating time is long, to be more advantageous to the formation of stably dispersing and composite material, is more conducive to
Improve ion reaction and ultrasonic cavitation effect.Lasting stirring and ultrasonication simultaneously, stirring purpose are real using strong stirring
The dispersion of existing ferrous ion generates effective ionization effect with the oxygen-containing group of surface of graphene oxide, is ferroso-ferric oxide
The combination of nanoparticle provides mass efficient combination target spot；Ultrasonic purpose is the high-energy generated using ultrasound, in mixed solution
Inside generates a large amount of bubbles, and bubbles burst improves maximum system energy, reduces activation energy required for reacting, promote ferrous iron from
The combination of son and graphene oxide.
The present invention uses divalent iron salt for single source of iron, under conditions of specific temperature and stirring ultrasound, Fe2+With oxidation
Ion reaction occurs for the oxygen-containing group (carboxyl, hydroxyl etc.) of graphene surface, and the two with ionic bond initially to be combined, with ultrasound
The progress of reaction, GO/ ferrous iron mixed salt solution is interior to be generated a large amount of bubbles and ruptures rapidly, cavitation bring caused by ultrasound
Energy, which sharply increases, promotes Fe2+Nano-scale particle is being formed with graphene oxide junction, meanwhile, it is anti-that GO carries out redox
It answers, generates ferroso-ferric oxide.And during specific ultrasonic reaction, maximum system energy is greatly increased, graphene surface atom
It absorbs energy to increase, so that Fe2+Rapider in conjunction with graphene oxide, a large amount of nano-scale particles are in surface of graphene oxide
It is formed, nano particle close-packed arrays, forms class " file surface " structure, surface of graphene oxide is made to become firm, it can be effective
The dispersion between lamella is solved,
Aqueous slkali is finally added in the present invention into the semi-finished product that above-mentioned steps obtain, and after carrying out thermostatic ultrasonic processing, obtains
Graphene oxide/ferriferrous oxide composite material.
The present invention is the configuration and compact uniform, above-mentioned step for improving ferroferric oxide nano granules in surface of graphene oxide
Suddenly it is particularly preferred as: aqueous slkali being added into the semi-finished product that above-mentioned steps obtain, after carrying out thermostatic ultrasonic processing, add surface
Activating agent carries out after being ultrasonically treated again, obtains graphene oxide/ferriferrous oxide composite material.
The selection of the aqueous slkali is not particularly limited in the present invention, is used for graphene with well known to those skilled in the art
The aqueous slkali of solution, those skilled in the art can select according to practical condition, product requirement and quality requirement
It selects and adjusts, aqueous slkali of the present invention preferably includes ammonium hydroxide and/or sodium hydroxide；The concentration of the aqueous slkali is preferably 1~
10mol/L, more preferably 3~8mol/L, more preferably 5~6mol/L, most preferably 1mol/L.The present invention is living to the surface
The selection of property agent is not particularly limited, with conventional surfactant well known to those skilled in the art, those skilled in the art
Member can be selected and be adjusted according to practical condition, product requirement and quality requirement, surfactant of the present invention
Preferably nonionic surface active agent, more preferably polyvinylpyrrolidone (PVP) or polyethylene glycol, more preferably different points
The polyvinylpyrrolidone (PVP) of son amount or the polyethylene glycol of different molecular weight, are particularly preferred as the poly- second of molecular weight 2000
Alkene pyrrolidone, the polyethylene glycol of molecular weight 1000, the polyethylene glycol of molecular weight 2000 or molecular weight 600 polyethylene glycol.This
The concentration of the surfactant is not particularly limited in invention, dense with conventional surfactant well known to those skilled in the art
Degree, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The concentration for inventing the surfactant is preferably 0.00005~0.0005mol/L, more preferably 0.00007~
0.0003mol/L, more preferably 0.00009~0.0001mol/L.
The temperature of thermostatic ultrasonic processing of the present invention is preferably 75~100 DEG C, and more preferably 35~65 DEG C, more preferably
40~60 DEG C, most preferably 45~55 DEG C；The frequency of thermostatic ultrasonic processing is 20~60KHz, more preferably 25~
55KHz, more preferably 30~50KHz, most preferably 40KHz；The time of the thermostatic ultrasonic processing is preferably 90~150min,
More preferably 100~140min, more preferably 110~130min, most preferably 115~125min.
The temperature of the present invention being ultrasonically treated again is preferably 75~100 DEG C, and more preferably 35~65 DEG C, more preferably
40~60 DEG C, most preferably 45~55 DEG C；Ultrasonic treatment again of the present invention preferably stirring ultrasonic treatment；It is of the present invention
The frequency being ultrasonically treated again be 20~60KHz, more preferably 25~55KHz, more preferably 30~50KHz, most preferably
40KHz；The time being ultrasonically treated again is preferably 90~150min, more preferably 100~140min, more preferably 110
~130min, most preferably 115~125min.
In graphene oxide/ferriferrous oxide composite material of the present invention, the definition of the graphene oxide is without spy
It does not limit, with definition well known to those skilled in the art, those skilled in the art can determine according to the case where raw material
Justice, according to the difference on raw material, graphene oxide may include other a variety of concepts such as graphene or Graphene derivative, base
It may be considered graphene oxide in raw material, the present invention.Equally, the concept of heretofore described graphene is also the stone of broad sense
Black alkene concept may include other a variety of concepts such as graphene oxide or Graphene derivative.
The present invention finally carries out the stirring ultrasonic treatment of specific frequency simultaneously within specified temperatures again, promotes ferrous iron
Salt generates ferroferric oxide nano granules with air effect under alkaline condition, and stirring then promotes to disperse, and realizes that particle is uniformly given birth to
Long, ultrasound reacts required energy to reduce, and uniform products is obtained, to be more advantageous to the excellent suction of stably dispersing and composite material
Wave performance is more conducive to improve overall process dispersion and compound effect.
After undergoing the above-described steps, it is also preferable to include washing Magneto separate and vacuum drying steps by the present invention；The present invention is to institute
The detailed process and condition for stating washing separating step are not particularly limited, with washing well known to those skilled in the art separation and magnetic
The process and condition of step are selected, those skilled in the art can be according to practical condition, product requirement and quality requirement
It is selected and is adjusted.The detailed process and condition of the vacuum drying step is not particularly limited in the present invention, with this field
The detailed process and condition of vacuum drying step known to technical staff, those skilled in the art can be according to actual productions
Situation, product requirement and quality requirement are selected and are adjusted, and vacuum drying temperature of the present invention is preferably 40~80 DEG C,
More preferably 45~75 DEG C, more preferably 50~70 DEG C, most preferably 55~65 DEG C；The vacuum drying time is preferably 4
~12h, more preferably 6~10h, most preferably 7~9h.
The present invention also provides a kind of absorbing materials, including graphite oxide prepared by above-mentioned technical proposal any one
Alkene/ferriferrous oxide composite material.
The concrete form and form of the absorbing material is not particularly limited in the present invention, known to those skilled in the art
Absorbing material, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, contain or be only the present invention prepared by graphene oxide/ferriferrous oxide composite material.It is provided by the invention
Graphene oxide/ferriferrous oxide composite material or absorbing material all have absorbing property, and can be for different suction waves
Graphene oxide/ferriferrous oxide composite material of frequency range or with it is different inhale wave frequency sections absorbing materials.
Ferroso-ferric oxide/graphene oxide composite nano wave-absorbing material has been prepared by above-mentioned steps in the present invention.This
Invention uses only heating and the condition of ultrasound is not needing any reducing agent by specific heating temperature and ultrasonic step
Under the conditions of, obtain graphene oxide/ferriferrous oxide composite material, Fe in the present invention2+It is oxygen-containing with surface of graphene oxide
Ion reaction occurs for group (carboxyl, hydroxyl etc.), and the two with ionic bond initially to be combined, and with the progress of ultrasonic reaction, GO/ is sub-
A large amount of bubbles are generated in molysite mixed solution and are ruptured rapidly, and cavitation bring energy caused by ultrasound, which sharply increases, to be promoted
Fe2+Nano-scale particle is being formed with graphene oxide junction.And during specific ultrasonic reaction, maximum system energy is significantly
Increase, surface of graphene oxide Atomic absorption energy increases, so that Fe2+In rapider in conjunction with graphene oxide, great Liang Na
Scale particles are formed in surface of graphene oxide, and the space constraint in conjunction with 2000 macromolecular of polyvinylpyrrolidone acts on, and are received
The even closer arrangement of rice grain forms class " file surface " structure, graphene surface is made to become firm.
Meanwhile the present invention passes through above-mentioned specific dispersion condition and step, moreover it is possible to effectively graphene sheet layer is avoided to reunite,
Obtain that lamella is uniform, the evenly dispersed composite material of surface particles, the dispersion between effective solution graphene sheet layer,
Realize the evenly dispersed dispersion between graphene sheet layer of ferroferric oxide nano granules on the surface of graphene.
Referring to Fig. 5, Fig. 5 is the transmission electron microscope picture of graphene oxide/ferriferrous oxide composite material prepared by the present invention；Ginseng
See that Fig. 6, Fig. 6 are the transmission electron microscope picture of graphene oxide/ferriferrous oxide composite material prepared by the present invention.It can by Fig. 5 and Fig. 6
Know, graphene oxide/ferriferrous oxide composite material provided by the present invention realizes uniform between graphene oxide layer
Dispersion.
In addition, preparation method simple process provided by the invention, mild condition, do not use any reducing agent catalyst, no
Impurity is introduced, the discharge of waste can be effectively reduced, safety and environmental protection is more suitable for scale industrial production, has centainly
Economic benefit and social benefit.
Importantly, the present invention can be prepared by the additional amount of adjusting divalent source of iron with different suction wave frequencies
Graphene oxide/ferriferrous oxide composite material of section.The experimental results showed that graphene oxide prepared by the present invention/tetra- oxidations
Three iron composite materials have excellent absorbing property, and the suction wave frequency section of composite material changes hair with the additional amount of divalent iron salt
Raw offset, realizes the electro-magnetic wave absorption of different frequency range.
In order to further illustrate the present invention, with reference to embodiments to provided by the invention a kind of with different suction wave frequency sections
Graphene oxide/ferriferrous oxide composite material preparation method be described in detail, but it is to be understood that these implementation
Example is to be implemented under the premise of the technical scheme of the present invention, and the detailed implementation method and specific operation process are given,
It is only further explanation the features and advantages of the present invention, rather than limiting to the claimed invention, protection of the invention
Range is also not necessarily limited to following embodiments.
Embodiment 1
One, graphene oxide water solution is prepared, and it is molten that the dispersion of 0.1mg/ml graphene oxide is obtained after ultrasonic disperse processing
Liquid；Compound concentration is the ferrous sulfate aqueous solution of 0.2mol/L again；
Two, the graphene oxide dispersion solution of step 1 is heated to 50 DEG C and continual ultrasonic 30min, by ferrous sulfate water
Solution is slowly dropped to graphene oxide dispersion solution, and rate of addition 5ml/min obtains precursor mixed solution；
Three, the precursor mixed solution of step 2 is heated to 90 DEG C and continual ultrasonic 30min, is added 30ml's
The sodium hydrate aqueous solution of 0.1mol/L, regulation system pH value are 10；
Four, after reaction system is maintained at 90 DEG C and continual ultrasonic reaction 120min, reaction product is obtained, rear Magneto separate is multiple
It is dried in vacuo 8h at 60 DEG C later, obtained black powder is ferroso-ferric oxide/graphene oxide composite material.
Graphene oxide/ferriferrous oxide composite material prepared by the present invention is analyzed,
Referring to Fig. 1, Fig. 1 is the X-ray diffractogram of graphene oxide/ferriferrous oxide composite material prepared by the present invention
Spectrum.As shown in Figure 1, the graphene composite wave-suction material that load has ferroso-ferric oxide has successfully been prepared in the present invention.
Referring to fig. 2, Fig. 2 is graphene oxide/ferriferrous oxide composite material scanning electricity prepared by the embodiment of the present invention 1
Sub- microscope photo.As shown in Figure 2, the uniform compact surface for being supported on graphene of ferroferric oxide nano granules, four oxidations
Three-iron nanoparticle size is in 20~30nm or so.
It is graphene oxide/ferriferrous oxide composite material transmission electricity prepared by the embodiment of the present invention 1 referring to Fig. 3, Fig. 3
Sub- microscope photo.From the figure 3, it may be seen that graphene sheet layer is sprawled as plane, ferroferric oxide nano granules are evenly distributed on up and down
Surface forms class " file surface " structure.
The composite material that the embodiment of the present invention 1 is prepared uniformly is mixed with solid paraffin 4:6 in mass ratio again, is utilized
Special die is compressed into the coaxial style of outer diameter 7.0mm, internal diameter 3.0mm, thickness 3.0mm, using model Agilent
N5234A vector network analyzer tests absorbing property,
Referring to fig. 4, Fig. 4 is the microwave reflection attenuation curve figure of absorbing material prepared by the present invention.As shown in Figure 4, it tests
Frequency is 2~18GHz, and it is -18.2dB that absorption maximum is reached in 6.85GHz, reach in 6~8.5GHz frequency range interior suction wave -
10dB is hereinafter, effectively absorbing width is 2.5GHz.
Embodiment 2
One, graphene oxide water solution is prepared, and it is molten that the dispersion of 0.1mg/ml graphene oxide is obtained after ultrasonic disperse processing
Liquid, compound concentration are the ferrous sulfate aqueous solution of 0.4mol/L；
Two, the graphene oxide dispersion solution of step 1 is heated to 50 DEG C and continual ultrasonic 30min, by ferrous sulfate water
Solution is slowly dropped to graphene oxide dispersion solution, and rate of addition 8ml/min obtains precursor mixed solution；
Three, the precursor mixed solution of step 2 is heated to 90 DEG C and continual ultrasonic 30min, is added 30ml's
The sodium hydrate aqueous solution of 0.1mol/L, regulation system pH value are 10；
Four, the reaction solution of step 3 is maintained at 90 DEG C, the polyethylene glycol 2000 of the 0.1mmol/L of 20ml is added dropwise
Aqueous solution；
Five, after reaction system is maintained at 90 DEG C and continual ultrasonic reaction 120min, reaction product is obtained, rear Magneto separate is multiple
It is dried in vacuo 8h at 60 DEG C later, obtained black powder is graphene oxide/ferriferrous oxide composite material.
Ferroso-ferric oxide/graphene oxide composite material prepared by the present invention is analyzed,
Referring to Fig. 1, Fig. 1 is the X-ray diffractogram of graphene oxide/ferriferrous oxide composite material prepared by the present invention
Spectrum.
As shown in Figure 1, the graphene composite wave-suction material that load has ferroso-ferric oxide has successfully been prepared in the present invention.
The composite material that the embodiment of the present invention 1 is prepared uniformly is mixed with solid paraffin 4:6 in mass ratio again, is utilized
Special die is compressed into the coaxial style of outer diameter 7.0mm, internal diameter 3.0mm, thickness 3.0mm, using model Agilent
N5234A vector network analyzer tests absorbing property,
Referring to fig. 4, Fig. 4 is the microwave reflection attenuation curve figure of absorbing material prepared by the present invention.As shown in Figure 4, it tests
Frequency is 2~18GHz, reaches maximum in 8.84GHz, absorption maximum is -20.3dB, in 7.4~10GHz frequency range interior suction wave
Reach -10dB hereinafter, effectively absorbing width is 2.6GHz.
Embodiment 3
One, graphene oxide water solution is prepared, and it is molten that the dispersion of 0.1mg/ml graphene oxide is obtained after ultrasonic disperse processing
Liquid, compound concentration are the ferrous chloride aqueous solution of 0.2mol/L；
Two, the graphene oxide dispersion solution of step 1 is heated to 50 DEG C and continual ultrasonic 30min, by protochloride molten iron
Solution is slowly dropped to graphene oxide dispersion solution, and rate of addition 5ml/min obtains precursor mixed solution；
Three, the precursor mixed solution of step 2 is heated to 90 DEG C and continual ultrasonic 30min, is added 30ml's
The ammonia spirit of 0.1mol/L, regulation system pH value are 10；
Four, the reaction solution of step 3 is maintained at 90 DEG C, the polyethylene glycol 2000 of the 0.1mmol/L of 20ml is added dropwise
Aqueous solution；
Five, after reaction system is maintained at 90 DEG C and continual ultrasonic reaction 120min, reaction product is obtained, rear Magneto separate is multiple
It is dried in vacuo 8h at 60 DEG C later, obtained black powder is graphene oxide/ferriferrous oxide composite material.
Referring to Fig. 1, Fig. 1 is the X-ray diffractogram of graphene oxide/ferriferrous oxide composite material prepared by the present invention
Spectrum.
As shown in Figure 1, the graphene composite wave-suction material that load has ferroso-ferric oxide has successfully been prepared in the present invention.Again
The composite material that the embodiment of the present invention 1 is prepared uniformly is mixed with solid paraffin 4:6 in mass ratio, it will using special die
Its coaxial style for being pressed into outer diameter 7.0mm, internal diameter 3.0mm, thickness 3.0mm, using model Agilent N5234A vector
Network Analyzer tests absorbing property,
Referring to fig. 4, Fig. 4 is the microwave reflection attenuation curve figure of absorbing material prepared by the present invention.As shown in Figure 4, it tests
Frequency is 2~18GHz, reaches maximum in 10.28GHz, absorption maximum is -34.95dB, in 5.72~7.88GHz frequency range
It inhales wave and reaches -10dB hereinafter, effectively absorbing width is 2.1GHz.
A kind of preparation method of graphene oxide/ferriferrous oxide composite material provided by the invention has been carried out in detail above
Thin introduction, used herein a specific example illustrates the principle and implementation of the invention, above embodiments
Illustrate to be merely used to help understand method and its core concept of the invention, including best mode, and but also this field
Any technical staff can practice the present invention, including any device or system of manufacture and use, and implement the side of any combination
Method.It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, may be used also
With several improvements and modifications are made to the present invention, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The range of the invention patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other realities
Apply example.If these other embodiments, which have, is not different from the structural element of claim character express, or if they
Equivalent structural elements including the character express with claim without essence difference, then these other embodiments should also be included in
In the scope of the claims.
Claims (9)
1. a kind of preparation method of graphene oxide/ferriferrous oxide composite material, which is characterized in that comprise the steps of:
A) by graphene oxide solution after ultrasonic disperse, graphene oxide dispersion is obtained；
B) graphene oxide dispersion for obtaining above-mentioned steps adds ferrous iron by heating with after second of ultrasonic disperse
Source obtains precursor mixed solution；
The temperature of the heating is 30~70 DEG C；
The frequency of second of ultrasonic disperse is 20~60KHz；The time of second of ultrasonic disperse is 10~50min；
C) precursor mixed solution that above-mentioned steps obtain is heated and is ultrasonically treated again, obtains semi-finished product；
The temperature heated again is 75~100 DEG C；The time heated again is 90~150min；
The frequency of the ultrasonic treatment is 20~60KHz；The time of the ultrasonic treatment is 10~50min；
D aqueous slkali) is added into the semi-finished product that above-mentioned steps obtain, after carrying out thermostatic ultrasonic processing, obtains graphene oxide/tetra-
Fe 3 O composite material；
The temperature of the thermostatic ultrasonic processing is 75~100 DEG C；The frequency of the thermostatic ultrasonic processing is 20~60KHz；It is described
The time of thermostatic ultrasonic processing is 90~150min.
2. preparation method according to claim 1, which is characterized in that the concentration of the graphene oxide solution be 0.5~
1.5mg/mL；
The divalent source of iron is ferrous salt solution；
The ferrous salt includes one of ferrous sulfate, frerrous chloride and ferrous nitrate or a variety of；
The concentration of the ferrous salt solution is 0.005~0.03mol/L.
3. preparation method according to claim 1, which is characterized in that change the additional amount of the divalent source of iron, the oxygen
Graphite alkene/ferriferrous oxide composite material is with the different graphene oxide/ferriferrous oxide composite materials for inhaling wave frequency section.
4. preparation method according to claim 1, which is characterized in that the step D) specifically: it is obtained to above-mentioned steps
Semi-finished product in be added aqueous slkali, after carrying out thermostatic ultrasonic processing, add surfactant and carry out after being ultrasonically treated again, obtain
To graphene oxide/ferriferrous oxide composite material.
5. preparation method according to claim 1, which is characterized in that the step B) in, it is described to add slowly to drip
Add, the speed being slowly added dropwise is 1~10mL/min.
6. preparation method according to claim 1, which is characterized in that the aqueous slkali includes ammonium hydroxide and/or sodium hydroxide；
The concentration of the aqueous slkali is 1~10mol/L.
7. the preparation method according to claim 4, which is characterized in that the temperature being ultrasonically treated again is 75~100
℃；The frequency being ultrasonically treated again is 20~60KHz, and the time being ultrasonically treated again is 90~150min.
8. the preparation method according to claim 4, which is characterized in that further include that vacuum is dry after the ultrasonic treatment again
Dry step；
The vacuum drying temperature is 40~80 DEG C, and the vacuum drying time is 4~12h.
9. a kind of absorbing material, which is characterized in that including graphene oxide prepared by claim 1~8 any one/tetra- oxygen
Change three iron composite materials.
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| CN107369821A (en) * | 2017-07-18 | 2017-11-21 | 中国石油大学(华东) | A kind of ultrafast method for preparing ferroso-ferric oxide/graphene lithium ion battery composite negative pole material |
| CN107418513B (en) * | 2017-07-21 | 2020-04-07 | 大连理工大学 | Graphene foam loaded nano Fe3O4Magnetic particle composite wave-absorbing material and preparation method thereof |
| 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 |
| CN110066070A (en) * | 2019-04-30 | 2019-07-30 | 秾源科技(北京)有限公司 | A kind of method and application using residual hydrogen peroxide autoxidation treatment of pulp waste liquid |
| CN110398180B (en) * | 2019-08-13 | 2022-04-26 | 杨婷 | Reflection type stealth method based on graphene super surface |
| CN110669315B (en) * | 2019-10-08 | 2022-04-22 | 西北工业大学 | Preparation method of hybrid nano paper/EP/CF wave-absorbing composite material |
| CN110745813A (en) * | 2019-10-21 | 2020-02-04 | 上海船舶工程质量检测有限公司 | Graphene-loaded ferroferric oxide magnetic powder particle and preparation method thereof |
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