CN113831894A - Ferrite graphene composite material and preparation method thereof - Google Patents
Ferrite graphene composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 151
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 55
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005119 centrifugation Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 229940046149 ferrous bromide Drugs 0.000 claims description 2
- -1 ferrous carboxylate Chemical class 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 229940076136 ferrous iodide Drugs 0.000 claims description 2
- 229960001781 ferrous sulfate Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 2
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 claims description 2
- 239000002932 luster Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims 1
- 239000004323 potassium nitrate Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 239000011358 absorbing material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000011668 ascorbic acid Substances 0.000 description 4
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- 239000002114 nanocomposite Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 230000003595 spectral effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
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- 238000000089 atomic force micrograph Methods 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
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- 238000005187 foaming Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention provides a ferrite graphene composite material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, dispersing potassium permanganate and graphite powder in concentrated sulfuric acid, and reacting to obtain a graphite oxide sheet; s2, cleaning the graphite oxide sheet, stirring in the cleaning process, peeling the graphite oxide sheet into graphene oxide through centrifugation, and forming a stable graphene oxide suspension in water; s3, adding soluble ferrous salt and nickel salt into the graphene oxide suspension; s4, heating the mixed solution in the step S3 in a reaction kettle to 160-200 ℃, and preserving heat for 8-12 hours; s5, adding a reducing agent into the cooled mixed solution obtained in the step S4, treating the mixture in an oven at 70-80 ℃ for at least 72 hours, and reducing graphene oxide into reduced graphene oxide; and S6, separating and washing the sample reacted in the step S5, and fully drying to obtain the ferrite graphene composite material.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a ferrite graphene composite material and a preparation method thereof.
Background
Graphene is a periodic honeycomb two-dimensional carbon new material formed by arranging sp2 hybridized carbon atoms in a hexagon, the thickness of the graphene is only 0.335nm, and the graphene has excellent electrical, thermal and mechanical properties. The graphene has a single atomic layer structure, stable property, large specific surface area, high conductivity and lower density than the traditional carbon material, and is an ideal wave absorber and wave absorbing carrier. The ferrite wave-absorbing material is composed of iron element, oxygen element and a series of metal elements with different valence states. The ferrite wave-absorbing material has the advantages of simple preparation, low production cost and good wave-absorbing performance, and although the ferrite wave-absorbing material has the defects of high material density, insufficient thermal stability and the like, the ferrite wave-absorbing material is still the most widely and mature wave-absorbing material researched and used in the traditional wave-absorbing material.
The precursor, namely graphite oxide, commonly used for preparing graphene by a wet chemical method is easy to obtain, has low cost, large specific surface area and abundant surface functional groups, can be compounded with other inorganic nano particles to form a functionalized graphene composite material by reduction, and has great application potential in the fields of electronic devices, energy storage, biomedicine and the like. At present, the application of the ferrite graphene composite material is going to be practically applied from a laboratory. Graphene-metal nanocomposites are generally prepared by water/solvothermal methods, coprecipitation methods, and sol-gel methods, and related laboratory preparation processes have been matured. In consideration of industrial preparation of mass production, an efficient and environment-friendly preparation process needs to be found, and mass production is realized through a simple process on the premise of ensuring stable material performance.
Disclosure of Invention
In order to overcome the defects in the prior art, the inventor carries out intensive research and provides a ferrite graphene composite material and a preparation method thereof, graphene oxide is prepared based on an improved Hummers method, a strong oxidant is used for oxidizing crystalline flake graphite, a series of oxidation functional groups such as hydroxyl, epoxy, carboxyl and the like are inserted between graphite layers, the graphite layer spacing is increased, and graphite oxide with a thin-layer structure, fewer layers and oxygen-containing functional groups such as carboxyl is prepared; and then stripping graphite by a centrifugal method to obtain few-layer or even single-layer graphene oxide. The present invention has been accomplished by reducing graphene oxide to graphene having high conductivity and good stability using a reducing agent, and converting ferrous ions, as an iron source, into ferrite nanoparticles to obtain a ferrite/graphene composite material.
The technical scheme provided by the invention is as follows:
in a first aspect, a preparation method of a ferrite graphene composite material comprises the following steps:
s1, dispersing potassium permanganate and graphite powder in concentrated sulfuric acid, and reacting to obtain a graphite oxide sheet;
s2, cleaning the graphite oxide thin slices, stirring in the cleaning process, peeling the graphite oxide thin slices into graphene oxide through centrifugation, and forming stable few-layer or single-layer graphene oxide suspension liquid in water;
s3, adding soluble ferrous salt and nickel salt into the graphene oxide suspension;
s4, heating the mixed solution obtained in the step S3 in a reaction kettle to 160-200 ℃, and preserving heat for 8-12 hours;
s5, adding a reducing agent into the cooled mixed solution obtained in the step S4, treating the mixture in an oven at 70-80 ℃ for at least 72 hours, cooling the mixture to room temperature, and reducing graphene oxide into Reduced Graphene Oxide (RGO);
and S6, separating and washing the sample reacted in the step S5, and fully drying to obtain the ferrite graphene composite material.
In a second aspect, a ferrite graphene composite material is prepared by the preparation method of the ferrite graphene composite material of the first aspect, wherein in an XRD spectrogram of the ferrite graphene composite material, obvious nickel ferrite characteristic peaks exist at positions with 2 theta of 18.4 degrees, 30.3 degrees, 35.6 degrees, 43.3 degrees, 53.8 degrees, 57.2 degrees and 62.8 degrees, and the thickness of a graphene layer is nano-scale.
According to the ferrite graphene composite material and the preparation method thereof provided by the invention, the following beneficial effects are achieved:
(1) the graphene oxide prepared by the improved Hummers method has a good lamellar structure, the timeliness in the preparation process is relatively good, no virulent raw material is involved in the preparation process, and the preparation method is environment-friendly.
(2) The preparation process of the ferrite graphene is simple and easy to operate, and the preparation of the composite material with stable performance can be realized.
(3) The preparation process of the ferrite graphene is green, environment-friendly, harmless and pollution-free.
(4) The ferrite particle size in the ferrite graphene composite material can be controlled at a nanometer level, and the ferrite graphene composite material can have unique properties of nanometer materials.
(5) The electromagnetic property of the ferrite graphene composite material is related to the ratio of graphene to ferrite, and the ratio of graphene to ferrite raw materials, the amount of a reducing agent and the like are groped through the characterization of the electromagnetic property of the ferrite/graphene composite wave-absorbing material, so that the ferrite graphene composite material with good electromagnetic property is finally obtained.
Drawings
FIG. 1 is an AFM image of a graphene oxide sheet layer;
fig. 2 is SEM images of graphene oxide (a) and reduced graphene oxide (b);
fig. 3 is a raman spectrum of graphene oxide (a) and reduced graphene oxide (b);
FIG. 4 is an SEM image of a nickel oxy-ferrite/graphene nanocomposite;
fig. 5 is an XRD image of nickel ferrite;
fig. 6 is an XRD image of the ferrite/graphene composite.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
According to a first aspect of the present invention, a preparation method of a ferrite graphene composite material is provided, which comprises the following steps:
s1, dispersing potassium permanganate and graphite powder in concentrated sulfuric acid, and reacting to obtain a graphite oxide sheet;
s2, cleaning the graphite oxide thin slices, stirring in the cleaning process, peeling the graphite oxide thin slices into graphene oxide through centrifugation, and forming stable few-layer or single-layer graphene oxide suspension liquid in water;
s3, adding soluble ferrous salt and nickel salt into the graphene oxide suspension;
s4, heating the mixed solution obtained in the step S3 in a reaction kettle to 160-200 ℃, and preserving heat for 8-12 hours;
s5, adding a reducing agent into the cooled mixed solution obtained in the step S4, treating the mixture in an oven at 70-80 ℃ for at least 72 hours, cooling the mixture to room temperature, and reducing graphene oxide into Reduced Graphene Oxide (RGO);
and S6, separating and washing the sample reacted in the step S5, and fully drying to obtain the ferrite graphene composite material.
In a preferred embodiment, in step S1, the step of dispersing potassium permanganate and graphite powder in concentrated sulfuric acid to react to obtain graphite oxide flakes specifically includes the following steps: mixing natural crystalline flake graphite with KNO3Stirring and suspending in concentrated sulfuric acid, adding KMnO under the cooling of ice water4The reaction was allowed to proceed and the mixture was allowed to return to room temperature and stirring was continued for at least 3 days.
Wherein, the natural crystalline flake graphite and KNO3、KMnO4The volume ratio of mass (in grams) to concentrated sulfuric acid (in milliliters) of 5: 4.2-4.8: 20-25: 160-180, preferably 5: 4.4-4.6: 22-23: 165-175, more preferably 5: 4.5: 22.5: 169.
in a preferred embodiment, in step S2, the step of washing the graphite oxide flakes specifically includes the following steps:
s2.1, slowly dispersing the mixture obtained in the step S1 in 5-10 wt% of H2SO4Continuously stirring in the aqueous solution; then adding aqueous hydrogen peroxide solution, and continuing stirring for at least 1 hour; wherein the mass ratio of the natural crystalline flake graphite to the aqueous hydrogen peroxide solution is 5: 12-18, preferably 5: 14-16, more preferably 5: 15 aqueous hydrogen peroxide concentration at 30vol percent;
s2.2, using 3-4 wt% of H2SO4/0.5～0.6wt％H2O2Diluting, and stirring overnight;
s2.3, centrifuging the mixture at 8000-90000 revolutions per minute for 15-25 minutes, and separating to obtain viscous dark yellow liquid;
s2.4, after the viscous liquid is vigorously shaken for at least 5 minutes, circularly implementing the step S2.2-the step S2.3 for at least three times, wherein the luster of the viscous components is gradually reduced in the cleaning process, and the color is gradually darkened until no glitter can be seen in the cleaning process;
s2.5, continuously washing the mixture by pure water, and centrifugally separating the viscous liquid until the supernatant is neutral. This produced a dark brown viscous liquid Graphene Oxide (GO) that could be used directly in an aqueous suspension of GO (e.g. at a concentration of 3mg/ml) or the remaining water could be removed by high speed centrifugation (e.g. 20,000rpm,30 minutes) and vacuum drying.
In a preferred embodiment, in step S3, the soluble ferrous salt includes at least one of ferrous chloride, ferrous bromide, ferrous iodide, ferrous sulfate, ferrous nitrate, or soluble ferrous carboxylate; the nickel salt is nickel chloride hexahydrate.
In a preferred embodiment, in step S3, the soluble ferrous salt and the nickel salt are used in a ratio of (1.9 to 2.1):1, based on the amount of the positive metal ion.
In a preferred embodiment, in step S3, the ratio of graphene oxide to nickel ferrite is 1: (1.9-2.1), adding soluble ferrous salt and nickel salt into the graphene oxide suspension, wherein the nickel ferrite is nickel ferrite (NiFe)2O4)。
In a preferred embodiment, in step S5, the reducing agent is at least one selected from ascorbic acid, hydrazine hydrate or sodium borohydride, and is preferably ascorbic acid.
In a preferred embodiment, in step S5, the mass ratio of the reducing agent to the graphene oxide is (6-8): 1, preferably 7: 1.
In a second aspect, a ferrite graphene composite material is prepared by the preparation method of the ferrite graphene composite material of the first aspect, wherein in an XRD spectrogram of the ferrite graphene composite material, obvious nickel ferrite characteristic peaks exist at positions with 2 theta of 18.4 degrees, 30.3 degrees, 35.6 degrees, 43.3 degrees, 53.8 degrees, 57.2 degrees and 62.8 degrees, and the thickness of a graphene layer is nano-scale.
Examples
Example 1
Mixing natural crystalline flake graphite (5g) and KNO3(4.5g) was suspended in concentrated sulfuric acid (169ml) with stirring, the mixture was cooled in ice, and KMnO was added4(22.5g) for over 70 minutes, then the mixture was allowed to return to room temperature by stirring for 7 days.
The dark mixture was then slowly dispersed for 1 hour to 550ml of 5 wt% H2SO4The mixture was stirred for 3 hours. The hydrogen peroxide (15g,30 vol%) was added over 5 minutes with considerable foaming after addition and the mixture turned into a yellow/gold suspension which was stirred for an additional 2 hours. With 500ml of 3 wt% H2SO4/0.5wt％H2O2The mixture was diluted and stirred overnight. Thereafter, the resulting mixture is subjected to a washing process to obtain a graphene oxide suspension. The resulting mixture was centrifuged at 8000 rpm for 20 minutes, resulting in separation of the mixture into two approximately equal portions, with a small amount of very dark colored pellets (discarded), one of which was a clear supernatant (decanted and discarded) and the other was a viscous dark yellow liquid. The viscous liquid was then dispersed by vigorous shaking (5-10 minutes) to 500ml of 3 wt% H2SO4/0.5wt％H2O2The resulting mixture was washed 4 times, during which the gloss of the viscous component gradually decreased and the color gradually darkened, so that no glitter was visible by the fourth wash. The mixture was then washed with purified water (500ml) and concentrated by centrifugation (discarding the colourless supernatant) until the supernatant was neutral (pH 7). As shown in fig. 1, AFM results for graphene oxide indicate that the thickness of the material is 1.2nm, consistent with the thickness of single layer graphene in the literature.
To synthesize nickel ferrite (NiFe)2O4) First, 0.1M ferric chloride hexahydrate is prepared in 50ml of deionized water and stirred uniformly. Then under the same conditions, 0.1M nickel chloride hexahydrate solution was prepared in 25ml deionized water and stirred uniformly. Mixing and stirring the two solutions in a magnetic stirrer to form a precursor (the color is light yellow); mixing a graphene oxide solution (the mass ratio of graphene oxide to nickel ferrite is 1: 2) with the precursor, putting the mixture into a reaction kettle, and heating the mixture for 10 hours at the temperature of 180 ℃.
Adding a reducing agent ascorbic acid into the cooled mixed solution, wherein the addition amount of the ascorbic acid is 7 times of the mass of the graphene oxide, heating the mixed solution in an oven to 80 ℃, fully reacting for 72 hours, and reducing the graphene oxide into reduced graphene oxide after the reaction is finished; as shown in fig. 2, SEM images of graphene oxide (fig. a) and reduced graphene oxide (fig. b) show that the prepared graphene oxide and reduced graphene oxide have good lamellar structures. Fig. 3 is a raman spectrum of graphene oxide and reduced graphene oxide, and the ratio of the D-band peak to the G-band peak is increased, indicating that graphene oxide is chemically reacted and reduced to reduced graphene oxide.
And separating, washing and fully drying the reacted sample to obtain the ferrite graphene composite material. As shown in fig. 4, in the SEM image of the nickel ferrite/graphene nanocomposite, the group of nickel ferrite nanoparticles was covered by the graphene sheet layer, and the length was 200-400 nm. As shown in fig. 5 and 6, XRD images of nickel ferrite and ferrite/graphene composite materials, respectively. The XRD image of the ferrite/graphene composite material can observe the positions of 7 obvious spectral peaks, namely 18.4 degrees, 30.3 degrees, 35.6 degrees, 43.3 degrees, 53.8 degrees, 57.2 degrees and 62.8 degrees, which are consistent with the positions of the spectral peaks of the nickel ferrite and accord with the reflection characteristics of the spinel-type ferrite. At the same time, no characteristic diffraction peak of graphene oxide occurred, indicating that graphene oxide was reduced and that stacking of reduced graphene oxide lamellae did not occur. In addition, no other crystal spectrum peaks appear, which shows that the purity of the ferrite/graphene composite material is very high, and the preparation process of the ferrite/graphene nano composite material is feasible.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made in the technical solution of the present invention and the embodiments thereof without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.
Claims (10)
1. A preparation method of a ferrite graphene composite material is characterized by comprising the following steps:
s1, dispersing potassium permanganate and graphite powder in concentrated sulfuric acid, and reacting to obtain a graphite oxide sheet;
s2, cleaning the graphite oxide sheet, stirring in the cleaning process, peeling the graphite oxide sheet into graphene oxide through centrifugation, and forming a stable graphene oxide suspension in water;
s3, adding soluble ferrous salt and nickel salt into the graphene oxide suspension;
s4, heating the mixed solution obtained in the step S3 in a reaction kettle to 160-200 ℃, and preserving heat for 8-12 hours;
s5, adding a reducing agent into the cooled mixed solution obtained in the step S4, treating the mixture in an oven at 70-80 ℃ for at least 72 hours, cooling the mixture to room temperature, and reducing the graphene oxide into reduced graphene oxide;
and S6, separating and washing the sample reacted in the step S5, and fully drying to obtain the ferrite graphene composite material.
2. The method for preparing the ferrite graphene composite material according to claim 1, wherein in step S1, potassium permanganate (KMnO) is added4) And graphite powder are dispersed in concentrated sulfuric acid to react to obtain graphite oxide flakes, and the method specifically comprises the following steps: mixing natural crystalline flake graphite and potassium nitrate (KNO)3) Stirring and suspending in concentrated sulfuric acid, adding KMnO under the cooling of ice water4The reaction was allowed to proceed and the mixture was allowed to return to room temperature and stirring was continued for at least 3 days.
3. The method of preparing a ferrite graphene composite material according to claim 2, wherein the natural crystalline flake graphite, KNO3、KMnO4The volume ratio of mass (in grams) to concentrated sulfuric acid (in milliliters) of 5: 4.2-4.8: 20-25: 160-180 parts.
4. The method for preparing a ferrite graphene composite material according to claim 1, wherein in step S2, the step of cleaning the graphite oxide sheet specifically comprises the following steps:
s2.1, slowly dispersing the mixture obtained in the step S1 in 5-10 wt% of H2SO4Continuously stirring in the aqueous solution; then hydrogen peroxide (H) is added2O2) Continuing stirring the aqueous solution for at least 1 hour;
s2.2, using 3-4 wt% of H2SO4/0.5～0.6wt％H2O2Diluting, and stirring overnight;
s2.3, centrifuging the mixture at 8000-90000 revolutions per minute for 15-25 minutes, and separating to obtain viscous dark yellow liquid;
s2.4, circularly implementing the step S2.2-the step S2.3 for at least three times after the viscous liquid is greatly shaken, wherein the luster of the viscous components is gradually reduced in the cleaning process, and the color is gradually darkened until no glitter can be seen in the cleaning process;
s2.5, continuously washing the mixture by pure water, and centrifugally separating the viscous liquid until the supernatant is neutral.
5. The method for preparing a ferrite graphene composite material according to claim 4, wherein in step S2.1, the mass ratio of the natural crystalline flake graphite to the aqueous hydrogen peroxide solution is 5: 12 to 18, wherein the concentration of the aqueous hydrogen peroxide solution is 30 vol%.
6. The method for preparing a ferrite graphene composite material according to claim 1, wherein in step S3, the soluble ferrous salt includes at least one of ferrous chloride, ferrous bromide, ferrous iodide, ferrous sulfate, ferrous nitrate, or soluble ferrous carboxylate; the nickel salt is nickel chloride hexahydrate.
7. The method for preparing a ferrite graphene composite material according to claim 1, wherein in step S3, the soluble ferrous salt and the nickel salt are used in a ratio of (1.9-2.1): 1 in terms of the amount of positive valence metal ions.
8. The method for preparing a ferrite graphene composite material according to claim 1, wherein in step S3, the ratio of graphene oxide to nickel ferrite is 1: (1.9-2.1), adding soluble ferrous salt and nickel salt into the graphene oxide suspension, wherein the nickel ferrite is nickel ferrite (NiFe)2O4)。
9. The preparation method of the ferrite graphene composite material according to claim 1, wherein in step S5, the mass ratio of the reducing agent to the graphene oxide is (6-8): 1.
10. A ferrite graphene composite material, which is prepared by the preparation method of the ferrite graphene composite material according to any one of claims 1 to 9, wherein the XRD spectrum of the ferrite graphene composite material has distinct nickel ferrite characteristic peaks at 2 θ of 18.4 °, 30.3 °, 35.6 °, 43.3 °, 53.8 °, 57.2 ° and 62.8 °, and the thickness of the graphene layer is nanoscale.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114275820A (en) * | 2022-01-11 | 2022-04-05 | 南通金仕达超微阻燃材料有限公司 | NiFe2O4One-pot preparation method of few-layer graphite broadband wave-absorbing powder material |
| CN115521139A (en) * | 2022-10-18 | 2022-12-27 | 北京无线电测量研究所 | Graphene-garnet type ferrite composite material, preparation and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011087305A2 (en) * | 2010-01-13 | 2011-07-21 | 전남대학교산학협력단 | Method for producing pure graphene sheets using pva coagulation, and graphene sheets produced by the method |
-
2021
- 2021-08-13 CN CN202110932450.4A patent/CN113831894A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011087305A2 (en) * | 2010-01-13 | 2011-07-21 | 전남대학교산학협력단 | Method for producing pure graphene sheets using pva coagulation, and graphene sheets produced by the method |
Non-Patent Citations (3)
| Title |
|---|
| 李庆: "石墨烯基复合吸波材料的制备和性能", 《中国优秀学位论文全文数据库 工程科技I辑》, no. 2016, pages 7 * |
| 杨应昌: "《二维材料的制备及其在能源存储领域的应用研究》", 30 September 2019, 中国原子能出版社, pages: 28 - 29 * |
| 阳征会 等: "Ni-Zn铁氧体粉体的水热法制备与磁性研究", 《矿冶工程》, vol. 26, no. 4, pages 39 - 42 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114275820A (en) * | 2022-01-11 | 2022-04-05 | 南通金仕达超微阻燃材料有限公司 | NiFe2O4One-pot preparation method of few-layer graphite broadband wave-absorbing powder material |
| CN114275820B (en) * | 2022-01-11 | 2023-12-01 | 南通金仕达高精实业股份有限公司 | NiFe 2 O 4 One-pot preparation method of few-layer graphite broadband wave-absorbing powder material |
| CN115521139A (en) * | 2022-10-18 | 2022-12-27 | 北京无线电测量研究所 | Graphene-garnet type ferrite composite material, preparation and application |
| CN115521139B (en) * | 2022-10-18 | 2023-10-20 | 北京无线电测量研究所 | Graphene-garnet type ferrite composite material, preparation and application |
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