CN106118594A - 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
The invention provides the preparation method of a kind of graphene oxide/ferriferrous oxide composite material, a kind of preparation method with the different graphene oxide/ferriferrous oxide composite material inhaling ripple frequency range.The present invention, under conditions of only with heating and being ultrasonic, by specific heating and ultrasonic step, in the case of need not any reducing agent, has obtained graphene oxide/ferriferrous oxide composite material；And but composite ferroferric oxide nano granules close-packed arrays prepared by the present invention is dispersed, form class " file surface " structure, the most effectively solve the scattering problem between graphene sheet layer, it is achieved that ferroferric oxide nano granules is dispersed between the dispersed of graphenic surface and graphene sheet layer.The preparation method technique that the present invention provides is simple, mild condition, do not use any reducing agent catalyst, does not introduce impurity, can effectively reduce the discharge of garbage, safety and environmental protection, is more suitable for large-scale industrial and produces.
Description
Technical field
The invention belongs to absorbing material technical field, relate to the system of a kind of graphene oxide/ferriferrous oxide composite material
Preparation Method, particularly relates to a kind of preparation with the different graphene oxide/ferroso-ferric oxide composite wave-suction material inhaling ripple frequency range
Method.
Background technology
Electromagnetic pollution refers to the interference of natural and artificial various electromagnetic waves and harmful electromagnetic radiation.Due to broadcast, electricity
Depending on, the development of microwave technology, radio-frequency apparatus power is multiplied, and ground electromagnetic radiation increases considerably, and has reached direct
Threaten the degree of health.The mutual change in electric field and magnetic field produces electromagnetic wave.Electromagnetism wave direction air-launched or converge the showing of flood
As, make electromagnetic radiation, the electromagnetic radiation of excess result in electromagnetic pollution.
Along with developing rapidly of microwave and mechanics of communication, increasingly severe electromagnetic pollution is to environment and the threat of bio-safety
Day by day it is taken seriously.The harm that electromagnetic pollution is caused can not be underestimated, and in Modern Family, electromagnetic wave is being made for people
While good fortune, also with the effect of " electronic smoke ", it is detrimental to health directly or indirectly.Research finds, electromagnetic radiation pair
Public's health has the most potential threat and impact, and for a long time by electromagenetic wave radiation, human tissue organ can be by its long-term damage
Accumulation can occur pathological changes；The strong jamming of military installations, aviation the most also can be caused catastrophic effect by electromagnetic radiation.Therefore, newly
The absorbing material of type needs the electro-magnetic wave absorption ability in the widest electromagnetic regime with excellence, thickness to be had concurrently
Spend thin, light weight and the high characteristic of intensity.
Graphene is that one has bi-dimensional cellular shape nanostructured, the New Type of Carbon material being made up of single carbon atom close-packed arrays
Material, it has bigger specific surface area, good electric heating conductive performance.Meanwhile, Graphene has the highest dielectric constant, at electricity
Can be polarized by external magnetic field in magnetic field, and the internal electric dipole of grapheme material occurs relaxation with electric field motion, consumes part electricity
Can and make electrolyte itself generate heat, i.e. produce dielectric loss.Single graphene sheet layer is easily penetrated by electromagnetic wave and loses electromagnetism
Ripple absorbability, meanwhile, single high dielectric loss also results in the difficulty of impedance matching.By by Graphene and four oxidations three
Ferrum is combined, and electromagnetic wave can be made to penetrate after composite by potential barrier effect between quantum dot array and space steric effect
Hinder and delay being directed through of electromagnetic wave, thus play reduction wave frequency effect.Meanwhile, four oxygen of graphenic surface load
Change three iron nano-particles and can carry out electromagnetic wave absorption by mechanism such as magnetic hystersis loss, eddy-current loss and ferromagnetic resonances.Thus, oxidation
Graphene/ferriferrous oxide composite material receives the extensive concern of scholar in field.
But, the preparation method of existing graphene oxide/ferroso-ferric oxide composite wave-suction material needs to use water mostly
The noxious substances such as conjunction hydrazine are as reducing agent, and not only processing step is complicated, and the requirement to the equipment of production is the highest, it is difficult to realize
Large-scale production and application.In addition, the use of poisonous and harmful raw material there is also and pollutes environment and poison the latent of health
In risk.
Therefore, how to find the preparation method of a kind of more optimal graphene oxide/ferriferrous oxide composite material, make
Process conditions are gentle, safety and environmental protection, it has also become many manufacturers in the industry and line research staff major issue urgently to be resolved hurrily.
Summary of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of there is absorbing property graphene oxide/
The preparation method of ferriferrous oxide composite material, a kind of have different graphene oxide/tetra-oxidation three inhaling ripple frequency range
The preparation method of ferrum composite wave-suction material, the preparation method of graphene oxide/ferriferrous oxide composite material that the present invention provides
Technique is simple, mild condition, safety and environmental protection, is suitable for large-scale industrial production, but also enables to ferriferrous oxide particles
Dispersed in surface of graphene oxide and there is adjustable function, thus there is preferable absorbing property and different suction ripples frequency
Section.
The invention provides the preparation method of a kind of graphene oxide/ferriferrous oxide composite material, comprise the following steps:
A) by graphene oxide solution after ultrasonic disperse, graphene oxide dispersion is obtained；
B) graphene oxide dispersion above-mentioned steps obtained is after heating and second time ultrasonic disperse, adds two
Valency source of iron, obtains precursor mixed solution；
C) precursor mixed solution above-mentioned steps obtained heats and supersound process again, obtains semi-finished product；
D) in the semi-finished product that above-mentioned steps obtains, add aqueous slkali, after carrying out thermostatic ultrasonic process, obtain graphite oxide
Alkene/ferriferrous oxide composite material.
Preferably, the concentration of described graphene oxide solution is 0.5～1.5mg/mL；
Described bivalence source of iron is ferrous salt solution；
Described ferrous salt includes one or more in ferrous sulfate, ferrous chloride and ferrous nitrate；
The concentration of described ferrous salt solution is 0.005～0.03mol/L.
Preferably, changing the addition of described bivalence source of iron, described graphene oxide/ferriferrous oxide composite material is tool
There is the different graphene oxide/ferriferrous oxide composite material inhaling ripple frequency range.
Preferably, described step D) particularly as follows: add aqueous slkali in the semi-finished product that above-mentioned steps obtains, carry out constant temperature and surpass
After sonication, add after surfactant carries out again supersound process, obtain graphene oxide/ferroso-ferric oxide composite wood
Material.
Preferably, described step B) in, the temperature of described heating is 30～70 DEG C；
The frequency of described second time ultrasonic disperse is 20～60KHz, the time of described second time ultrasonic disperse be 10～
50min；
Described step B) in, described in add as being slowly added dropwise, described in the speed that is slowly added dropwise be 1～10mL/min.
Preferably, described step C) in, the described temperature again heated is 75～100 DEG C, the described time again heated
It is 90～150min；
The frequency of described supersound process is 20～60KHz, and the time of described supersound process is 10～50min.
Preferably, described aqueous slkali includes ammonia and/or sodium hydroxide；
The concentration of described aqueous slkali is 1～10mol/L.
Preferably, the temperature that described thermostatic ultrasonic processes is 75～100 DEG C；Described thermostatic ultrasonic process frequency be 20～
60KHz, the time that described thermostatic ultrasonic processes is 90～150min；
The temperature of described supersound process again is 75～100 DEG C；The frequency of described supersound process again is 20～60KHz,
The time of described supersound process again is 90～150min.
Preferably, after described supersound process again, vacuum drying step is also included；
Described vacuum drying temperature is 40～80 DEG C, and the described vacuum drying time is 4～12h.
Present invention also offers a kind of absorbing material, including the graphite oxide prepared by technique scheme any one
Alkene/ferriferrous oxide composite material.
The invention provides the preparation method of a kind of graphene oxide/ferriferrous oxide composite material, comprise the following steps,
First, by graphene oxide solution after ultrasonic disperse, graphene oxide dispersion is obtained；Then above-mentioned steps is obtained
Graphene oxide dispersion, after heating and second time ultrasonic disperse, adds bivalence source of iron, obtains precursor mixed solution；
Precursor mixed solution above-mentioned steps obtained again heats and supersound process again, obtains semi-finished product；Last to above-mentioned
The semi-finished product that step obtains add aqueous slkali, after carrying out thermostatic ultrasonic process, obtains graphene oxide/ferroso-ferric oxide and be combined
Material.Compared with prior art, the present invention is under conditions of only with heating and being ultrasonic, by specific heating and ultrasonic step,
Under conditions of need not any reducing agent, obtain graphene oxide/ferriferrous oxide composite material, it is often more important that, this
But the composite ferroferric oxide nano granules close-packed arrays of invention preparation is dispersed, form class " file surface " knot
Structure, effectively solves the scattering problem between graphene sheet layer, it is achieved that ferroferric oxide nano granules is at graphenic surface
Dispersed.The present invention fundamentally solves in existing preparation process, uses hydrazine hydrate, sodium borohydride or ascorbic acid
The reducing agents such as sodium, not only harm environment and production operation are healthy, but also there may be the defects such as impurities left, prepare simultaneously
Composite structure is imperfect, and nano-particle is mutually piled up, and dispersion inequality, the absorbing property etc. being substantially reduced composite is asked
Topic.The preparation method technique that the present invention provides is simple, mild condition, do not use any reducing agent catalyst, does not introduce impurity, energy
The effective discharge reducing garbage, safety and environmental protection, it is more suitable for large-scale industrial and produces, there is certain economic benefit and society
Benefit.Test result indicate that, ferroso-ferric oxide/graphene oxide composite material prepared by the present invention has the wave absorbtion of excellence
Can, and composite inhale ripple frequency range with divalent iron salt addition change offset, it is achieved the electromagnetic wave of different frequency range
Absorb.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of graphene oxide/ferriferrous oxide composite material prepared by the present invention；
Fig. 2 is the scanning electron microscope of the graphene oxide/ferriferrous oxide composite material of the embodiment of the present invention 1 preparation
Photo；
Fig. 3 is the transmission electron microscope of the graphene oxide/ferriferrous oxide composite material of the embodiment of the present invention 1 preparation
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.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but
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
Limit.
The all raw materials of the present invention, are not particularly limited its source, that commercially buy or according to people in the art
Prepared by the conventional method known to Yuan.
The all raw materials of the present invention, are not particularly limited its purity, use in present invention preferably employs analytical pure or field
Conventional purity.
The invention provides the preparation method of a kind of graphene oxide/ferriferrous oxide composite material, comprise the following steps:
A) by graphene oxide solution after ultrasonic disperse, graphene oxide dispersion is obtained；
B) graphene oxide dispersion above-mentioned steps obtained is after heating and second time ultrasonic disperse, adds two
Valency source of iron, obtains precursor mixed solution；
C) precursor mixed solution above-mentioned steps obtained heats and supersound process again, obtains semi-finished product；
D) in the semi-finished product that above-mentioned steps obtains, add aqueous slkali, after carrying out thermostatic ultrasonic process, obtain graphite oxide
Alkene/ferriferrous oxide composite material.
The present invention first by graphene oxide solution after ultrasonic disperse, obtain graphene oxide dispersion.The present invention
The source of described graphene oxide solution is not particularly limited, with preparation method well known to those skilled in the art preparation or city
Sell and buy.The concentration of described graphene oxide solution is not particularly limited by the present invention, knows with those skilled in the art
The normal concentration of graphene oxide solution, the concentration of graphene oxide solution of the present invention be 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 to described ultrasonic disperse of inventing is not particularly limited, and with the condition of ultrasonic disperse well known to those skilled in the art is
Can, those skilled in the art can select according to practical condition, product requirement and prescription and adjust.
The graphene oxide dispersion that then above-mentioned steps is obtained by the present invention through heating and second time ultrasonic disperse after,
Add bivalence source of iron, obtain precursor mixed solution.
Described bivalence source of iron is not particularly limited by the present invention, with bivalence source of iron well known to those skilled in the art,
Those skilled in the art can select according to practical condition, product requirement and prescription and adjust, and the present invention is excellent
Elect ferrous salt solution as, more preferably include one or more in ferrous sulfate, ferrous chloride and ferrous nitrate, more preferably bag
Include ferrous sulfate or ferrous chloride.The concentration of described ferrous salt solution is not particularly limited by the present invention, with people in the art
The concentration of the ferrous salt solution known to Yuan, those skilled in the art can be according to practical condition, product requirement and matter
Amount requirement selects and adjusts, and the concentration of ferrous salt solution of the present invention is preferably 0.005～0.03mol/L, more preferably
It is 0.01～0.025mol/L, most preferably 0.015～0.02mol/L.
The present invention uses bivalence source of iron as raw material, it is possible to achieve the suction ripple frequency range of composite is with the addition of bivalence source of iron
Amount change offsets, by changing described bivalence source of iron addition, it is achieved the electro-magnetic wave absorption of different frequency range；Of the present invention
Inhale ripple i.e. electromagnetic wave absorption；Described concrete suction ripple frequency range is not particularly limited by the present invention, and those skilled in the art can root
According to practical condition, suction ripple requires and described bivalence source of iron addition is selected and adjusts by prescription accordingly.
The mode of described addition is not particularly limited by the present invention, and those skilled in the art can be according to actual production feelings
Condition, product requirement and prescription select and adjust, and the present invention is for improving ion reaction and ultrasonic cavitation effect, described
Add and be preferably slowly added dropwise；The described 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 time ultrasonic disperse of the present invention be preferably 20～60KHz, more preferably 25～
55KHz, more preferably 30～50KHz, most preferably 40KHz；The time of described second time ultrasonic disperse be preferably 10～
50min, more preferably 15～45min, more preferably 20～40min, most preferably 25～35min.
The present invention carries out the ultrasonic of characteristic frequency and time the most simultaneously, is favorably improved ion reaction
And ultrasonic cavitation effect.
The precursor mixed solution that above-mentioned steps is obtained by the present invention subsequently heats and supersound process again, obtains half
Finished product；
The temperature again heated of the present invention is preferably 75～100 DEG C, more preferably 35～65 DEG C, more preferably 40～
60 DEG C, most preferably 45～55 DEG C；The time again heated of the present invention be preferably 90～150min, more preferably 100～
140min, more preferably 110～130min, most preferably 115～125min.
Supersound process of the present invention preferably stirs supersound process；The frequency of supersound process of the present invention is preferably 20
～60KHz, more preferably 25～55KHz, more preferably 30～50KHz, most preferably 40KHz；The time of described supersound process
Preferably 10～50min, more preferably 15～45min, more preferably 20～40min, most preferably 25～35min.
The present invention carries out the ultrasonic of characteristic frequency and time within specified temperatures, forms gradient variable with temperature before
Changing, the most above-mentioned ultrasonic time is short, and heat time heating time is long, to be more beneficial for the formation of stably dispersing and composite, is more conducive to
Improve ion reaction and ultrasonic cavitation effect.The most continuously stirred and ultrasonication, stirring purpose is to utilize strong stirring real
The dispersion of existing ferrous ion, produces effective ion effect, for ferroso-ferric oxide with the oxy radical of surface of graphene oxide
The combination of nanoparticle provides mass efficient to combine target spot；Ultrasonic purpose is to utilize the high-energy of ultrasonic generation, at mixed solution
Internal producing a large amount of bubbles, bubbles burst makes maximum system energy improve, reduces the activation energy required for reaction, promotion ferrous iron from
Son and the combination of graphene oxide.
The present invention uses divalent iron salt to be single source of iron, under conditions of specific temperature and stirring are ultrasonic, and Fe2+With oxidation
There is ion reaction in the oxy radical (carboxyl, hydroxyl etc.) of graphenic surface, both are initially to combine with ionic bond, with ultrasonic
The carrying out of reaction, produces a large amount of bubbles and ruptures rapidly in GO/ ferrous salt mixed solution, the ultrasonic cavitation caused is brought
Energy sharply increases and promotes Fe2+Forming nano-scale particle with graphene oxide junction, meanwhile, it is anti-that GO carries out oxidoreduction
Should, produce ferroso-ferric oxide.And during specific ultrasonic reaction, maximum system energy is greatly increased, graphenic surface atom
Absorption energy increases so that Fe2+More rapid being combined with graphene oxide, a large amount of nano-scale particles are in surface of graphene oxide
Formed, nano-particle close-packed arrays, form class " file surface " structure, make surface of graphene oxide become firm, can be effective
Solve the scattering problem between lamella,
The present invention finally adds aqueous slkali in the semi-finished product that above-mentioned steps obtains, and after carrying out thermostatic ultrasonic process, obtains
Graphene oxide/ferriferrous oxide composite material.
The present invention is to improve ferroferric oxide nano granules at the configuration of surface of graphene oxide and to compact uniformly, above-mentioned step
Suddenly it is particularly preferred as: in the semi-finished product that above-mentioned steps obtains, add aqueous slkali, after carrying out thermostatic ultrasonic process, add surface
After activating agent carries out again supersound process, obtain graphene oxide/ferriferrous oxide composite material.
The selection of described aqueous slkali is not particularly limited by the present invention, with well known to those skilled in the art for Graphene
The aqueous slkali of solution, those skilled in the art can select according to practical condition, product requirement and prescription
Selecting and adjust, aqueous slkali of the present invention preferably includes ammonia and/or sodium hydroxide；The concentration of described aqueous slkali be preferably 1～
10mol/L, more preferably 3～8mol/L, more preferably 5～6mol/L, most preferably 1mol/L.Lived in described surface by the present invention
The selection of property agent is not particularly limited, with conventional surfactant well known to those skilled in the art, people in the art
Member can select according to practical condition, product requirement and prescription and adjust, surfactant of the present invention
It is preferably nonionic surfactant, more preferably polyvinylpyrrolidone (PVP) or Polyethylene Glycol, more preferably difference point
Son amount polyvinylpyrrolidone (PVP) or different molecular weight Polyethylene Glycol, be 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 the Polyethylene Glycol of molecular weight 600.This
Invent the concentration to described surfactant to be not particularly limited, dense with conventional surfactant well known to those skilled in the art
Spending, those skilled in the art can select according to practical condition, product requirement and prescription and adjust, this
Invent the concentration of described surfactant be preferably 0.00005～0.0005mol/L, more preferably 0.00007～
0.0003mol/L, more preferably 0.00009～0.0001mol/L.
The temperature that thermostatic ultrasonic of the present invention processes is preferably 75～100 DEG C, more preferably 35～65 DEG C, more preferably
40～60 DEG C, most preferably 45～55 DEG C；Described thermostatic ultrasonic process frequency be 20～60KHz, more preferably 25～
55KHz, more preferably 30～50KHz, most preferably 40KHz；The time that described thermostatic ultrasonic processes is preferably 90～150min,
More preferably 100～140min, more preferably 110～130min, most preferably 115～125min.
The temperature of supersound process again of the present invention is preferably 75～100 DEG C, more preferably 35～65 DEG C, more preferably
40～60 DEG C, most preferably 45～55 DEG C；Supersound process again of the present invention preferably stirs supersound process；Of the present invention
The frequency of supersound process is 20～60KHz again, more preferably 25～55KHz, more preferably 30～50KHz, most preferably
40KHz；The time of described supersound process again is preferably 90～150min, more preferably 100～140min, and more preferably 110
～130min, most preferably 115～125min.
In graphene oxide/ferriferrous oxide composite material of the present invention, the definition of described graphene oxide does not has spy
Not limiting, define with well known to those skilled in the art, it is fixed that those skilled in the art can be carried out according to the situation of raw material
Justice, according to the difference on raw material, graphene oxide can comprise other many conceptions of species such as Graphene or Graphene derivative, base
Graphene oxide is may be considered in raw material, the present invention.Equally, the concept of heretofore described Graphene is also the stone of broad sense
Ink alkene concept, it can comprise other many conceptions of species such as graphene oxide or Graphene derivative.
The present invention finally carries out the stirring supersound process of characteristic frequency the most simultaneously, promotes ferrous iron
Salt generates ferroferric oxide nano granules in the basic conditions with air effect, and stirring then promotes dispersion, it is achieved granule is uniformly given birth to
Long, ultrasonic obtain uniform products to reduce the required energy of reaction, to be more beneficial for the excellent suction of stably dispersing and composite
Ripple performance, is more conducive to improve overall process dispersion and compound effect.
The present invention after undergoing the above-described steps, the most also includes washing Magneto separate and vacuum drying step；The present invention is to institute
Detailed process and the condition of stating washing separating step are not particularly limited, and separate and magnetic with washing well known to those skilled in the art
Selecting process and the condition of step, those skilled in the art can be according to practical condition, product requirement and prescription
Select and adjust.Detailed process and the condition of described vacuum drying step are not particularly limited, with this area by the present invention
The detailed process of the vacuum drying step known to technical staff and condition, those skilled in the art can be according to actual production
Situation, product requirement and prescription select and adjust, 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 described vacuum drying time is preferably 4
～12h, more preferably 6～10h, most preferably 7～9h.
Present invention also offers a kind of absorbing material, including the graphite oxide prepared by technique scheme any one
Alkene/ferriferrous oxide composite material.
Concrete form and the form of described absorbing material are not particularly limited by the present invention, know with those skilled in the art
Absorbing material, those skilled in the art can select according to practical condition, product requirement and prescription
And adjustment, containing or only graphene oxide/ferriferrous oxide composite material prepared by the present invention.The present invention provides
Graphene oxide/ferriferrous oxide composite material or absorbing material are respectively provided with absorbing property, and can be to have different suction ripple
Graphene oxide/the ferriferrous oxide composite material of frequency range or there is the different absorbing material inhaling ripple frequency range.
The present invention has prepared ferroso-ferric oxide/graphene oxide composite nano wave-absorbing material through above-mentioned steps.This
Invention use only heating and ultrasonic condition, by specific heating-up temperature and ultrasonic step, need not any reducing agent
Under the conditions of, obtain graphene oxide/ferriferrous oxide composite material, Fe in the present invention2+Oxygen-containing with surface of graphene oxide
There is ion reaction in group (carboxyl, hydroxyl etc.), both are initially to combine with ionic bond, and with the carrying out of ultrasonic reaction, GO/ is sub-
Producing a large amount of bubbles in iron salt mixed solution and rupture rapidly, the energy that the ultrasonic cavitation caused is brought sharply increases and promotes
Fe2+Nano-scale particle is being formed with graphene oxide junction.And during specific ultrasonic reaction, maximum system energy is significantly
Increasing, surface of graphene oxide Atomic Absorption energy increases so that Fe2+More rapid being combined with graphene oxide, great Liang Na
Scale particles is formed in surface of graphene oxide, in conjunction with the space constraint effect of polyvinylpyrrolidone 2000 macromole, receives
Rice grain more close-packed arrays, forms class " file surface " structure, makes graphenic surface become firm.
Meanwhile, the present invention is by above-mentioned specific dispersion condition and step, moreover it is possible to effectively avoid graphene sheet layer to reunite,
Obtain lamella uniform, the homodisperse composite of surface particles, effectively solve the scattering problem between graphene sheet layer,
Achieve ferroferric oxide nano granules dispersion between the dispersed of graphenic surface and graphene sheet layer.
See the transmission electron microscope picture that Fig. 5, Fig. 5 are graphene oxide/ferriferrous oxide composite material prepared by the present invention；Ginseng
See the transmission electron microscope picture that Fig. 6, Fig. 6 are graphene oxide/ferriferrous oxide composite material prepared by the present invention.Can by Fig. 5 and Fig. 6
Know, graphene oxide/ferriferrous oxide composite material provided by the present invention, it is achieved that uniform between graphene oxide lamella
Dispersion.
Additionally, the preparation method technique that the present invention provides is simple, mild condition, do not use any reducing agent catalyst, no
Introduce impurity, it is possible to the effective discharge reducing garbage, safety and environmental protection, be more suitable for large-scale industrial and produce, have certain
Economic benefit and social benefit.
The more important thing is, the present invention can prepare have different suction ripple frequency by regulating the addition of bivalence source of iron
Graphene oxide/the ferriferrous oxide composite material of section.Test result indicate that, graphene oxide/tetra-oxidation prepared by the present invention
Three iron composite materials have the absorbing property of excellence, and the ripple frequency range of inhaling of composite is sent out with the addition change of divalent iron salt
Raw skew, it is achieved the electro-magnetic wave absorption of different frequency range.
In order to further illustrate the present invention, below in conjunction with embodiment, the one that the present invention provides is had difference and inhale ripple frequency range
The preparation method of graphene oxide/ferriferrous oxide composite material be described in detail, but it is to be understood that these are implemented
Example is to implement under premised on technical solution of the present invention, gives detailed embodiment and concrete operating process,
Simply for further illustrating the features and advantages of the present invention rather than limiting to the claimed invention, the protection of the present invention
Scope is also not necessarily limited to following embodiment.
Embodiment 1
One, preparation graphene oxide water solution, and ultrasonic disperse obtains the dispersion of 0.1mg/ml graphene oxide after processing molten
Liquid；Compound concentration is the ferrous sulfate aqueous solution of 0.2mol/L again；
Two, the graphene oxide dispersion soln of step one is heated to 50 DEG C and continual ultrasonic 30min, by ferrous sulfate water
Solution is slowly dropped to graphene oxide dispersion soln, and rate of addition is 5ml/min, obtains precursor mixed solution；
Three, the precursor mixed solution of step 2 is heated to 90 DEG C and continual ultrasonic 30min, adds 30ml's
The sodium hydrate aqueous solution of 0.1mol/L, regulation system pH value is 10；
Four, after reaction system is maintained at 90 DEG C and continual ultrasonic reaction 120min, obtaining product, rear Magneto separate is repeatedly
Being vacuum dried 8h afterwards at 60 DEG C, the black powder obtained is ferroso-ferric oxide/graphene oxide composite material.
Graphene oxide/ferriferrous oxide composite material prepared by the present invention is analyzed,
See the X-ray diffractogram that Fig. 1, Fig. 1 are graphene oxide/ferriferrous oxide composite material prepared by the present invention
Spectrum.As shown in Figure 1, the present invention has successfully prepared the Graphene composite wave-suction material being loaded with ferroso-ferric oxide.
See the scanning electricity of graphene oxide/ferriferrous oxide composite material that Fig. 2, Fig. 2 are the embodiment of the present invention 1 preparation
Sub-microphotograph.As shown in Figure 2, what ferroferric oxide nano granules uniformly compacted is supported on the surface of Graphene, four oxidations
Three-iron nanoparticle size is 20～about 30nm.
See the transmission electricity of graphene oxide/ferriferrous oxide composite material that Fig. 3, Fig. 3 are the embodiment of the present invention 1 preparation
Sub-microphotograph.From the figure 3, it may be seen that graphene sheet layer is sprawled as plane, ferroferric oxide nano granules is evenly distributed on up and down
Surface, forms class " file surface " structure.
The composite embodiment of the present invention 1 prepared again uniformly mixes with hard paraffin 4:6 in mass ratio, utilizes
Special die is compressed into the coaxial style of external diameter 7.0mm, internal diameter 3.0mm, thickness 3.0mm, and employing model is Agilent
N5234A vector network analyzer, tests absorbing property,
See the microwave reflection attenuation curve figure that Fig. 4, Fig. 4 are absorbing material prepared by the present invention.As shown in Figure 4, test
Frequency is 2～18GHz, reaches absorption maximum when 6.85GHz for-18.2dB, inhale in 6～8.5GHz frequency ranges ripple reach-
Below 10dB, effectively absorbing width is 2.5GHz.
Embodiment 2
One, preparation graphene oxide water solution, and ultrasonic disperse obtains the dispersion of 0.1mg/ml graphene oxide after processing molten
Liquid, compound concentration is the ferrous sulfate aqueous solution of 0.4mol/L；
Two, the graphene oxide dispersion soln of step one is heated to 50 DEG C and continual ultrasonic 30min, by ferrous sulfate water
Solution is slowly dropped to graphene oxide dispersion soln, and rate of addition is 8ml/min, obtains precursor mixed solution；
Three, the precursor mixed solution of step 2 is heated to 90 DEG C and continual ultrasonic 30min, adds 30ml's
The sodium hydrate aqueous solution of 0.1mol/L, regulation system pH value is 10；
Four, the reaction solution of step 3 is maintained at 90 DEG C, is added dropwise over the Macrogol 2000 of the 0.1mmol/L of 20ml
Aqueous solution；
Five, after reaction system is maintained at 90 DEG C and continual ultrasonic reaction 120min, obtaining product, rear Magneto separate is repeatedly
Being vacuum dried 8h afterwards at 60 DEG C, the black powder obtained is graphene oxide/ferriferrous oxide composite material.
Ferroso-ferric oxide/graphene oxide composite material prepared by the present invention is analyzed,
See the X-ray diffractogram that Fig. 1, Fig. 1 are graphene oxide/ferriferrous oxide composite material prepared by the present invention
Spectrum.
As shown in Figure 1, the present invention has successfully prepared the Graphene composite wave-suction material being loaded with ferroso-ferric oxide.
The composite embodiment of the present invention 1 prepared again uniformly mixes with hard paraffin 4:6 in mass ratio, utilizes
Special die is compressed into the coaxial style of external diameter 7.0mm, internal diameter 3.0mm, thickness 3.0mm, and employing model is Agilent
N5234A vector network analyzer, tests absorbing property,
See the microwave reflection attenuation curve figure that Fig. 4, Fig. 4 are absorbing material prepared by the present invention.As shown in Figure 4, test
Frequency is 2～18GHz, reaches maximum when 8.84GHz, and its absorption maximum is-20.3dB, inhales ripple in 7.4～10GHz frequency ranges
Reaching below-10dB, effectively absorbing width is 2.6GHz.
Embodiment 3
One, preparation graphene oxide water solution, and ultrasonic disperse obtains the dispersion of 0.1mg/ml graphene oxide after processing molten
Liquid, compound concentration is the ferrous chloride aqueous solution of 0.2mol/L；
Two, the graphene oxide dispersion soln of step one is heated to 50 DEG C and continual ultrasonic 30min, by protochloride molten iron
Solution is slowly dropped to graphene oxide dispersion soln, and rate of addition is 5ml/min, obtains precursor mixed solution；
Three, the precursor mixed solution of step 2 is heated to 90 DEG C and continual ultrasonic 30min, adds 30ml's
The ammonia spirit of 0.1mol/L, regulation system pH value is 10；
Four, the reaction solution of step 3 is maintained at 90 DEG C, is added dropwise over the Macrogol 2000 of the 0.1mmol/L of 20ml
Aqueous solution；
Five, after reaction system is maintained at 90 DEG C and continual ultrasonic reaction 120min, obtaining product, rear Magneto separate is repeatedly
Being vacuum dried 8h afterwards at 60 DEG C, the black powder obtained is graphene oxide/ferriferrous oxide composite material.
See the X-ray diffractogram that Fig. 1, Fig. 1 are graphene oxide/ferriferrous oxide composite material prepared by the present invention
Spectrum.
As shown in Figure 1, the present invention has successfully prepared the Graphene composite wave-suction material being loaded with ferroso-ferric oxide.Again
The composite embodiment of the present invention 1 prepared uniformly mixes with hard paraffin 4:6 in mass ratio, utilizes special die to incite somebody to action
It is pressed into the coaxial style of external diameter 7.0mm, internal diameter 3.0mm, thickness 3.0mm, and using model is Agilent N5234A vector
Network Analyzer, tests absorbing property,
See the microwave reflection attenuation curve figure that Fig. 4, Fig. 4 are absorbing material prepared by the present invention.As shown in Figure 4, test
Frequency is 2～18GHz, reaches maximum when 10.28GHz, and absorption maximum is-34.95dB, in 5.72～7.88GHz frequency ranges
Inhaling ripple and reach below-10dB, effectively absorbing width is 2.1GHz.
Above the preparation method of a kind of graphene oxide/ferriferrous oxide composite material that the present invention provides is carried out in detail
Thin introduction, principle and the embodiment of the present invention are set forth by specific case used herein, above example
Method and the core concept thereof being only intended to help to understand the present invention is described, including best mode, and also makes this area
Any technical staff can put into practice the present invention, including manufacturing and using any device or system, and implements the side of any combination
Method.It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, also may be used
So that the present invention is carried out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
The scope of patent protection of the present invention is defined by the claims, and those skilled in the art can be included it is conceivable that other are real
Execute example.If these other embodiments have the structural element being not different from claim character express, if or they
Including with the character express of claim without the equivalent structural elements of essence difference, then these other embodiments also should be included in
In the range of claim.
Claims (10)
1. the preparation method of graphene oxide/ferriferrous oxide composite material, it is characterised in that comprise the following steps:
A) by graphene oxide solution after ultrasonic disperse, graphene oxide dispersion is obtained；
B) graphene oxide dispersion above-mentioned steps obtained is after heating and second time ultrasonic disperse, adds ferrous iron
Source, obtains precursor mixed solution；
C) precursor mixed solution above-mentioned steps obtained heats and supersound process again, obtains semi-finished product；
D) in the semi-finished product that above-mentioned steps obtains, add aqueous slkali, after carrying out thermostatic ultrasonic process, obtain graphene oxide/tetra-
Fe 3 O composite.
Preparation method the most according to claim 1, it is characterised in that the concentration of described graphene oxide solution be 0.5～
1.5mg/mL；
Described bivalence source of iron is ferrous salt solution；
Described ferrous salt includes one or more in ferrous sulfate, ferrous chloride and ferrous nitrate；
The concentration of described ferrous salt solution is 0.005～0.03mol/L.
Preparation method the most according to claim 1, it is characterised in that change the addition of described bivalence source of iron, described oxygen
Functionalized graphene/ferriferrous oxide composite material is to have the different graphene oxide/ferriferrous oxide composite material inhaling ripple frequency range.
Preparation method the most according to claim 1, it is characterised in that described step D) particularly as follows: obtain to above-mentioned steps
Semi-finished product in add aqueous slkali, after carrying out thermostatic ultrasonic process, add after surfactant carries out again supersound process,
To graphene oxide/ferriferrous oxide composite material.
Preparation method the most according to claim 1, it is characterised in that described step B) in, the temperature of described heating is 30
～70 DEG C；
The frequency of described second time ultrasonic disperse is 20～60KHz, and the time of described second time ultrasonic disperse is 10～50min；
Described step B) in, described in add as being slowly added dropwise, described in the speed that is slowly added dropwise be 1～10mL/min.
Preparation method the most according to claim 1, it is characterised in that described step C) in, the described temperature again heated
Being 75～100 DEG C, the described time again heated is 90～150min；
The frequency of described supersound process is 20～60KHz, and the time of described supersound process is 10～50min.
Preparation method the most according to claim 1, it is characterised in that described aqueous slkali includes ammonia and/or sodium hydroxide；
The concentration of described aqueous slkali is 1～10mol/L.
Preparation method the most according to claim 4, it is characterised in that the temperature that described thermostatic ultrasonic processes is 75～100
℃；The frequency that described thermostatic ultrasonic processes is 20～60KHz, and the time that described thermostatic ultrasonic processes is 90～150min；
The temperature of described supersound process again is 75～100 DEG C；The frequency of described supersound process again is 20～60KHz, described
The time of supersound process is 90～150min again.
Preparation method the most according to claim 4, it is characterised in that after described supersound process again, also includes that vacuum is done
Dry step；
Described vacuum drying temperature is 40～80 DEG C, and the described vacuum drying time is 4～12h.
10. an absorbing material, it is characterised in that include graphene oxide/tetra-prepared by claim 1～9 any one
Fe 3 O composite.
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