CN114464782A - Amorphous iron oxide nanoparticle/multilayer graphene composite material and preparation method thereof - Google Patents
Amorphous iron oxide nanoparticle/multilayer graphene composite material and preparation method thereof Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 148
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 103
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 13
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 239000012153 distilled water Substances 0.000 claims description 21
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- -1 iron ions Chemical class 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- 229940031182 nanoparticles iron oxide Drugs 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000004698 iron complex Chemical class 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 239000007773 negative electrode material Substances 0.000 abstract 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 235000013980 iron oxide Nutrition 0.000 description 66
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 8
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 1
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention discloses an amorphous iron oxide nanoparticle/multilayer graphene composite material and a preparation method thereof. The preparation process of the composite material comprises the following steps: taking a mixed solvent of DMF and water as a solvent of a reaction system, adding expanded graphene, preparing multilayer graphene by an ultrasonic method, and adding FeCl2And EDTA-2Na, reacting for 2 hours under the condition of constant temperature of 90 ℃ by magnetic stirring, cooling, and then centrifugally cleaning and drying to obtain the composite material. The iron oxide particles in the composite material are amorphous, have small size and very high electrochemical activity, and the multilayer graphene can provide a conductive network, so that the composite material has potential application in the aspects of super capacitor negative electrode materials and lithium ion battery negative electrode materials.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an amorphous iron oxide nanoparticle/multilayer graphene composite material and a preparation method thereof.
Background
Iron oxides having a variety of crystal structures, including alpha-Fe2O3、β-Fe2O3、γ-Fe2O3FeO and Fe3O4And the like. Iron oxides are used in many fields, such as: super capacitor, lithium ion battery, gas sensor, magnetic material, pigment and catalyst. Different crystal structures and particle sizes have a large impact on the properties of iron oxides. In applications such as electrode materials, sensors, and catalysts, the reduction of the particle and grain size of iron oxides can increase the surface area of the material and increase the chemical reactivity of the material. Thus, nano-sized iron oxides are currently the focus of research. However, as the particle size decreases, the agglomeration of iron oxides becomes more and more severe, ultimately resulting in a decrease in their performance. Loading iron oxide onto other surfaces may prevent agglomeration of iron oxide nanoparticles. The composite material is compounded with graphene, so that the agglomeration of iron oxide can be reduced, and the defect of poor self-conductivity of the graphene can be overcome through the good conductivity of the graphene. Therefore, the research of the composite preparation of the nano iron oxide particles and the graphene becomes the focus of the current research.
Studies have shown that amorphous iron oxide (non-crystalline) has superior electrochemical properties compared to various crystalline iron oxides. Amorphous iron oxide has a low gibbs free energy of reaction; the disordered arrangement of iron atoms has better activity than the crystallized ferric oxide; no grain boundaries; the electrolyte diffuses more easily therein. Therefore, the compounding research of partial amorphous iron oxide and graphene is carried out. However, the current preparation techniques are complex. Meanwhile, the currently adopted carbon substrate material uses graphene oxide. The graphene oxide has some active groups on the surface, so that the surface activity of the graphene is improved, and the metal oxide nanoparticles can be compounded through the action of chemical bonds of the graphene oxide. However, the graphene oxide preparation process is complex, and the preparation process causes certain pollution to the environment. The carbon material with complete carbon ring has good chemical stability on the surface, and the oxide nano particles prepared on the surface are very difficult to agglomerate. Therefore, the preparation of the composite material on the surface of the graphene which is not oxidized is of great significance.
In order to overcome the defects of the prior art, the invention adopts multilayer graphene prepared by ultrasonic as a substrate. Although the chemical method has been reported to prepare the iron oxide nanoparticles on the surface of the multilayer graphene, the method cannot prepare amorphous iron oxide with more excellent performance on the surface of the multilayer graphene. How to make the generated iron oxide amorphous and make the amorphous uniformly distributed on the surface of the multilayer graphene becomes a problem to be solved.
Disclosure of Invention
Aiming at the problems in the background technology, the invention provides an amorphous iron oxide nanoparticle/multilayer graphene composite material and a preparation method thereof, wherein amorphous iron oxide particles are uniformly distributed on multilayer graphene.
In order to solve the technical problems in the prior art, the technical scheme of the invention is as follows:
the composite material takes multilayer graphene with the surface not activated prepared by an ultrasonic method as a substrate, and the amorphous iron oxide nanoparticles uniformly cover the surface of the multilayer graphene.
The invention also discloses a preparation method of the amorphous iron oxide nanoparticle/multilayer graphene composite material, which comprises the following steps:
step S1: weighing expanded graphite, measuring DMF (dimethyl formamide) and distilled water with a volume ratio of 8:2 as a mixed solvent, sequentially adding the mixed solvent into a reaction glass bottle, standing for 12 hours at room temperature, and then carrying out ultrasonic treatment for 4 hours to obtain a multilayer graphene solution A. The concentration of the multilayer graphene relative to a mixed solvent of DMF and water is 1-2 g/L.
Step S2: weighing EDTA-2Na and FeCl in an amount of 0.5-2 g/L and 10-20 g/L relative to the mixed solvent2Adding the multilayer graphene solution A, and magnetically stirring for 10 minutes to obtain a uniform mixed solution B.
Step S3: and (3) putting the mixed solution B into a water bath kettle, and reacting for 2 hours under the condition of constant temperature of 90 ℃ by magnetic stirring.
Step S4: after the reaction, the reaction mixture was cooled to room temperature, and centrifuged 3 times with absolute ethanol and distilled water to obtain solid powder C.
Step S5: and (3) putting the solid powder C obtained by centrifugation into a drying oven, and drying for 24 hours at 70 ℃ to obtain the amorphous iron oxide/multilayer graphene composite material.
The amorphous iron oxide nanoparticle/multilayer graphene composite material is prepared by the technical scheme, and the preparation principle is as follows: when EDTA-2Na is not added into the reaction solution, crystalline alpha-type Fe with the particle size of more than 100nm is obtained on the surface of the multilayer graphene2O3And the particles are not uniform in size and distribution. When the amount of EDTA-2Na added to the reaction solution exceeds 3g/L, almost no iron oxide is deposited on the surface of the multilayer graphene. According to the invention, the uniformly distributed amorphous iron oxide particles can be obtained on the surface of the multilayer graphene by adding the EDTA-2 Na. Thus: EDTA-2Na helps iron ions to be adsorbed to the surface of the multilayer graphene, and helps the iron ions to form amorphous iron oxide with small particle size.
EDTA-2Na can chelate iron ions and Fe2O3Has strong interference effect on crystallization and growth, and can prevent Fe2O3Crystallization and growth, or of Fe2O3Disorder of lattice arrangement and final Fe2O3An amorphous state is formed.
The Fe ion forms a complex with DMF and water. Multilayer graphene watchThe iron complex is adsorbed and captured by the surface under the action of molecular force. The complex is gradually decomposed on the surface of the multilayer graphene and is converted into Fe under the action of oxygen in water2O3. EDTA-2Na can chelate iron ions and Fe2O3Has strong interference effect on crystallization and growth, and can prevent Fe2O3Crystallization and growth, or of Fe2O3Disorder of lattice arrangement and final Fe2O3An amorphous state is formed. However, when a large amount of EDTA-2Na is added, EDTA-2Na complexes with all iron ions, so that Fe ions cannot form a complex with DMF and water, and thus, iron oxide particles cannot be formed on the surface of multilayer graphene.
Compared with the prior art, the invention has the following beneficial effects:
1. amorphous Fe prepared by the invention2O3a/MLG composite material. The iron oxide particles are amorphous, the particle size is small, and the chemical performance of the iron oxide is high.
2. The multilayer graphene forms a conductive network, so that the conductivity of the composite material is improved.
3. The amorphous ferric oxide nano-particles can uniformly cover the surface of the multilayer graphene, and the electron transfer speed between the ferric oxide and the multilayer graphene is high.
4. The multilayer graphene substrate is obtained by an ultrasonic method, and the amorphous iron oxide/multilayer graphene composite material is prepared by a one-step chemical method, so that the composite material is simple in preparation process, low in cost and beneficial to mass production.
5. When the composite material is used for lithium batteries and sodium ion batteries, the amorphous iron oxide nanoparticles can accommodate more electrochemical active sites, provide more transmission channels for ions, facilitate electron transfer and effectively buffer the volume change of the main body material in the charging and discharging processes.
6. When used in a supercapacitor, amorphous iron oxide can exhibit superior electrochemical properties due to its high degree of structural disorder, as compared to crystalline materials. The material disclosed by the invention has potential application in the aspects of super capacitor cathode materials, lithium ion battery cathode materials, sensors and catalysts.
Drawings
Fig. 1 low-magnification SEM image (a) and high-magnification SEM image (b) of amorphous iron oxide/multi-layered graphene obtained in example 1 of the present invention;
FIG. 2 XRD representation of amorphous iron oxide/multilayer graphene obtained in example 1 of the present invention;
fig. 3 low-magnification SEM image (a) and high-magnification SEM image (b) of amorphous iron oxide/multi-layered graphene obtained in example 2 of the present invention;
FIG. 4 XRD representation of amorphous iron oxide/multilayer graphene obtained in example 2 of the present invention;
FIG. 5 TEM image of amorphous iron oxide/multilayer graphene obtained in example 2 of the present invention;
fig. 6 low-magnification SEM image (a) and high-magnification SEM image (b) of amorphous iron oxide/multi-layered graphene obtained in example 3 of the present invention;
FIG. 7 XRD characterization of amorphous iron oxide/multilayer graphene obtained in example 3 of the present invention;
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
In order to uniformly distribute amorphous iron oxide particles on multilayer graphene, the invention provides a preparation method of an amorphous iron oxide nanoparticle/multilayer graphene composite material, which comprises the following steps:
step S1: weighing expanded graphite, measuring DMF (dimethyl formamide) and distilled water with a volume ratio of 8:2 as a mixed solvent, sequentially adding the mixed solvent into a reaction glass bottle, standing for 12 hours at room temperature, and then carrying out ultrasonic treatment for 4 hours to obtain a multilayer graphene solution A. The concentration of the multilayer graphene relative to a mixed solvent of DMF and water is 1-2 g/L.
Step S2: weighing EDTA-2Na and FeCl in an amount of 0.5-2 g/L and 10-20 g/L relative to the mixed solvent2Adding the multilayer graphene solution A, and magnetically stirring for 10 minutes to obtain a uniform mixed solution B.
Step S3: and (3) putting the mixed solution B into a water bath kettle, and reacting for 2 hours under the condition of constant temperature of 90 ℃ by magnetic stirring.
Step S4: after the reaction, the reaction mixture was cooled to room temperature, and centrifuged 3 times with absolute ethanol and distilled water to obtain solid powder C.
Step S5: and (3) putting the solid powder C obtained by centrifugation into a drying oven, and drying for 24 hours at 70 ℃ to obtain the amorphous iron oxide/multilayer graphene composite material.
The technical scheme is that the amorphous iron oxide nanoparticle/multilayer graphene composite material is prepared, multilayer graphene with the surface not activated prepared by an ultrasonic method is used as a substrate, and amorphous iron oxide nanoparticles are uniformly covered on the surface of the multilayer graphene. The preparation principle is as follows: when EDTA-2Na is not added into the reaction solution, crystalline alpha-type Fe with the particle size of more than 100nm is obtained on the surface of the multilayer graphene2O3And the particles are not uniform in size and distribution. When the amount of EDTA-2Na added to the reaction solution exceeds 3g/L, almost no iron oxide is deposited on the surface of the multilayer graphene. According to the invention, the uniformly distributed amorphous iron oxide particles can be obtained on the surface of the multilayer graphene by adding the EDTA-2 Na. Thus: EDTA-2Na helps iron ions to be adsorbed to the surface of the multilayer graphene, and helps the iron ions to form amorphous iron oxide with small particle size.
EDTA-2Na can chelate iron ions and Fe2O3Has strong interference effect on crystallization and growth, and can prevent Fe2O3Crystallization and growth, or of Fe2O3Disorder of lattice arrangement and final Fe2O3An amorphous state is formed.
The Fe ion forms a complex with DMF and water. The iron ion complex is adsorbed and captured on the surface of the multilayer graphene through the action of molecular force. The complex is gradually decomposed on the surface of the multilayer graphene and is converted into Fe under the action of oxygen in water2O3. EDTA-2Na can chelate iron ions and Fe2O3Has strong interference effect on crystallization and growth, and can prevent Fe2O3Crystallization and growth, or of Fe2O3Disorder of lattice arrangement and final Fe2O3An amorphous state is formed. However, after adding a large amount of EDTA-2Na, EDTA-2Na complexes with all the iron ions, making it impossible for Fe ions to form a complex with DMF and water, and thereforeIron oxide particles cannot be formed on the surface of the multilayer graphene.
The technical solution of the present invention is further illustrated by the following specific examples.
Specific example 1:
(1) preparing a multilayer graphene solution. Weighing 20mg of expanded graphite, adding the expanded graphite into a glass bottle, weighing 8mL of DMF (dimethyl formamide) and 2mL of distilled water by using a measuring cylinder, adding the DMF and the distilled water into the bottle, standing for 12 hours at room temperature, and carrying out ultrasonic treatment for 4 hours to obtain a multilayer graphene solution.
(2) Preparing the amorphous ferric oxide composite material. 5mg of EDTA-2Na and 100mg of FeCl were weighed2Adding a multilayer graphene solution, and magnetically stirring for 10min to obtain a uniform mixed solution.
(3) And (3) putting the mixed solution into a water bath kettle, and reacting for 2 hours under the condition of constant temperature of 90 ℃ by magnetic stirring.
(4) After the reaction result, it was cooled to room temperature and centrifuged 3 times with absolute ethanol and distilled water.
(5) And (3) putting the solid powder obtained by centrifugation into a drying oven, and drying for 24 hours at 70 ℃ to obtain the amorphous iron oxide/multilayer graphene composite material.
The scanning image of the amorphous iron oxide/multilayer graphene obtained in example 1 is shown in fig. 1, wherein fig. 1(a) is a low-magnification SEM image thereof, and fig. 1(b) is a high-magnification SEM image thereof. It can be seen from the figure that the surface of the multilayer graphene is uniformly covered with a layer of amorphous iron oxide particles. The XRD pattern of the amorphous iron oxide/multilayer graphene obtained in example 1 is shown in fig. 2. As can be seen from the figure, the diffraction peak at 26.6 ° is the (002) diffraction peak of carbon. In addition, no other significant diffraction peak was found, indicating that the iron oxide formed was amorphous.
Specific example 2:
(1) preparing a multilayer graphene solution. Weighing 20mg of expanded graphite, adding the expanded graphite into a glass bottle, weighing 8mL of DMF (dimethyl formamide) and 2mL of distilled water by using a measuring cylinder, adding the DMF and the distilled water into the bottle, standing for 12 hours at room temperature, and carrying out ultrasonic treatment for 4 hours to obtain a multilayer graphene solution.
(2) Preparing the amorphous ferric oxide composite material. 10mg of EDTA-2Na and 100mg of FeCl were weighed2Adding multilayer grapheneAnd magnetically stirring the solution for 10min to obtain a uniform mixed solution.
(3) And (3) putting the mixed solution into a water bath kettle, and reacting for 2 hours under the condition of constant temperature of 90 ℃ by magnetic stirring.
(4) After the reaction result, it was cooled to room temperature and centrifuged 3 times with absolute ethanol and distilled water.
(5) And (3) putting the solid powder obtained by centrifugation into a drying oven, and drying for 24 hours at 70 ℃ to obtain the amorphous iron oxide/multilayer graphene composite material.
The scanning image of the amorphous iron oxide/multi-layer graphene obtained in example 2 is shown in fig. 3, wherein fig. 3(a) is a low-magnification SEM image thereof, and fig. 3(b) is a high-magnification SEM image thereof. It can be seen from the figure that the surface of the multilayer graphene is uniformly covered with the grain size of a layer of amorphous iron oxide. The XRD pattern of the amorphous iron oxide/multilayer graphene obtained in example 2 is shown in fig. 4. As can be seen from the figure, the diffraction peaks at 26.6 ° and 53.6 ° are the (002) and (004) diffraction peaks of carbon. In addition, no other distinct diffraction peaks were found, indicating that the iron oxide formed was amorphous. A TEM image of the resulting amorphous iron oxide/multilayer graphene of example 2 is shown in fig. 5. As can be seen from fig. 5, the particle size of the iron oxide is less than 3 nm. The inset in fig. 5 is a high resolution TEM image of iron oxide, from which it can be seen that the lattice arrangement of amorphous iron oxide is disordered, indicating that the iron oxide is amorphous.
Specific example 3:
(1) preparing a multilayer graphene solution. Weighing 20mg of expanded graphite, adding the expanded graphite into a glass bottle, weighing 8mL of DMF (dimethyl formamide) and 2mL of distilled water by using a measuring cylinder, adding the DMF and the distilled water into the bottle, standing for 12 hours at room temperature, and carrying out ultrasonic treatment for 4 hours to obtain a multilayer graphene solution.
(2) Preparing the amorphous ferric oxide composite material. 20mg of EDTA-2Na and 100mg of FeCl were weighed2Adding a multilayer graphene solution, and magnetically stirring for 10min to obtain a uniform mixed solution.
(3) And (3) putting the mixed solution into a water bath kettle, and reacting for 2 hours under the condition of constant temperature of 90 ℃ by magnetic stirring.
(4) After the reaction result, it was cooled to room temperature and centrifuged 3 times with absolute ethanol and distilled water.
(5) And (3) putting the solid powder obtained by centrifugation into a drying oven, and drying for 24 hours at 70 ℃ to obtain the amorphous iron oxide/multilayer graphene composite material.
A scan of the amorphous iron oxide/multi-layer graphene obtained in example 3 is shown in fig. 6, where fig. 6(a) is a low-power SEM image thereof and fig. 6(b) is a high-power SEM image. As can be seen from the figure, the amorphous iron oxide has a certain agglomeration, the appearance is spherical, and larger gaps are formed among the spheres. The XRD pattern of the amorphous iron oxide/multilayer graphene obtained in example 3 is shown in fig. 7. As can be seen from the figure, the diffraction peaks at 26.6 ° and 53.6 ° are the (002) and (004) diffraction peaks of carbon. In addition, no other distinct diffraction peaks were found, indicating that the iron oxide produced was still amorphous.
Specific example 4:
(1) preparing a multilayer graphene solution. Weighing 10mg of expanded graphite, adding the expanded graphite into a glass bottle, weighing 8mL of DMF (dimethyl formamide) and 2mL of distilled water by using a measuring cylinder, adding the DMF and the distilled water into the bottle, standing for 12 hours at room temperature, and carrying out ultrasonic treatment for 4 hours to obtain a multilayer graphene solution.
(2) Preparing the amorphous ferric oxide composite material. 10mg of EDTA-2Na and 100mg of FeCl were weighed2Adding a multilayer graphene solution, and magnetically stirring for 10min to obtain a uniform mixed solution.
(3) And (3) putting the mixed solution into a water bath kettle, and reacting for 2 hours under the condition of constant temperature of 90 ℃ by magnetic stirring.
(4) After the reaction result, it was cooled to room temperature and centrifuged 3 times with absolute ethanol and distilled water.
(5) And (3) putting the solid powder obtained by centrifugation into a drying oven, and drying for 24 hours at 70 ℃ to obtain the amorphous iron oxide/multilayer graphene composite material.
Specific example 5:
(1) preparing a multilayer graphene solution. Weighing 20mg of expanded graphite, adding the expanded graphite into a glass bottle, weighing 8mL of DMF (dimethyl formamide) and 2mL of distilled water by using a measuring cylinder, adding the DMF and the distilled water into the bottle, standing for 12 hours at room temperature, and carrying out ultrasonic treatment for 4 hours to obtain a multilayer graphene solution.
(2) Preparing the amorphous ferric oxide composite material. 10mg of EDTA-2Na and 200mg of FeCl were weighed2Incorporating multi-layered graphiteAnd magnetically stirring the alkene solution for 10min to obtain a uniform mixed solution.
(3) And (3) putting the mixed solution into a water bath kettle, and reacting for 2 hours under the condition of constant temperature of 90 ℃ by magnetic stirring.
(4) After the reaction result, it was cooled to room temperature and centrifuged 3 times with absolute ethanol and distilled water.
(5) And (3) putting the solid powder obtained by centrifugation into a drying oven, and drying for 24 hours at 70 ℃ to obtain the amorphous iron oxide/multilayer graphene composite material.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The amorphous iron oxide nanoparticle/multilayer graphene composite material is characterized in that multilayer graphene with an unactivated surface prepared by an ultrasonic method is used as a substrate, and amorphous iron oxide nanoparticles uniformly cover the surface of the multilayer graphene.
2. A preparation method of an amorphous iron oxide nanoparticle/multilayer graphene composite material is characterized by comprising the following steps:
step S1: weighing expanded graphite, measuring DMF (dimethyl formamide) and distilled water with a volume ratio of 8:2 as a mixed solvent, sequentially adding the mixed solvent into a reaction glass bottle, standing for 12 hours at room temperature, and then carrying out ultrasonic treatment for 4 hours to obtain a multilayer graphene solution A; the concentration of the multilayer graphene relative to a mixed solvent of DMF and water is 1-2 g/L;
step S2: weighing EDTA-2Na and FeCl in an amount of 0.5-2 g/L and 10-20 g/L relative to the mixed solvent2Adding the multilayer graphene solution A, and magnetically stirring for 10 minutes to obtain a uniform mixed solution B;
step S3: putting the mixed solution B into a water bath kettle, and reacting for 2 hours under the condition of constant temperature of 90 ℃ by magnetic stirring;
step S4: after the reaction is finished, cooling to room temperature, and centrifuging for 3 times by using absolute ethyl alcohol and distilled water respectively to obtain solid powder C;
step S5: and (3) putting the solid powder C obtained by centrifugation into a drying oven, and drying for 24 hours at 70 ℃ to obtain the amorphous iron oxide/multilayer graphene composite material.
3. The method for preparing the amorphous iron oxide nanoparticle/multilayer graphene composite material according to claim 2, wherein a complex is formed by Fe ions, DMF and water, and the iron complex is adsorbed and captured on the surface of the multilayer graphene by the action of molecular force; the complex is gradually decomposed on the surface of the multilayer graphene and is converted into Fe under the action of oxygen in water2O3。
4. The method of claim 2, wherein the added EDTA-2Na facilitates the adsorption of iron ions onto the surface of the multi-layer graphene.
5. The method of claim 4, wherein the EDTA-2Na chelates iron ions and couples Fe2O3Has strong interference effect on the crystallization and growth of Fe to prevent Fe2O3Crystallization and growth of Fe2O3An amorphous state is formed.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016158806A1 (en) * | 2015-03-27 | 2016-10-06 | 富士化学工業株式会社 | Novel composite of iron compound and graphene oxide |
| CN109243832A (en) * | 2018-08-06 | 2019-01-18 | 杭州电子科技大学 | A kind of α type Fe2O3Nano particle/multi-layer graphene composite material preparation method |
| US20190273255A1 (en) * | 2016-10-20 | 2019-09-05 | Agency For Science, Technology And Research | A method for preparing metal oxide nanosheets |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016158806A1 (en) * | 2015-03-27 | 2016-10-06 | 富士化学工業株式会社 | Novel composite of iron compound and graphene oxide |
| US20190273255A1 (en) * | 2016-10-20 | 2019-09-05 | Agency For Science, Technology And Research | A method for preparing metal oxide nanosheets |
| CN109243832A (en) * | 2018-08-06 | 2019-01-18 | 杭州电子科技大学 | A kind of α type Fe2O3Nano particle/multi-layer graphene composite material preparation method |
Non-Patent Citations (2)
| Title |
|---|
| DAN LI等: ""Amorphous Fe2O3/Graphene Composite Nanosheets with Enhanced Electrochemical Performance for Sodium-Ion Battery"", 《ACS APPL. MATER. INTERFACES》, vol. 8, pages 30899 * |
| XIAOMING ZHU等: ""Fe2O3amorphous nanoparticles/graphene composite as high-performance anode materials for lithium-ion batteries"", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 711, pages 15 - 21, XP029988116, DOI: 10.1016/j.jallcom.2017.03.235 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116425499A (en) * | 2023-04-20 | 2023-07-14 | 锦丞环保科技材料(六安)有限公司 | Fiber reinforced gypsum product with anion release function and preparation method thereof |
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