CN110065938B - Preparation method of structurally-ordered graphene/Fe 3O4 aerogel - Google Patents
Preparation method of structurally-ordered graphene/Fe 3O4 aerogel Download PDFInfo
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- CN110065938B CN110065938B CN201910460382.9A CN201910460382A CN110065938B CN 110065938 B CN110065938 B CN 110065938B CN 201910460382 A CN201910460382 A CN 201910460382A CN 110065938 B CN110065938 B CN 110065938B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B32/00—Carbon; Compounds thereof
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- C01G49/00—Compounds of iron
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- C01G49/08—Ferroso-ferric oxide (Fe3O4)
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/42—Magnetic properties
Abstract
The invention discloses a graphene/Fe with an ordered structure3O4The preparation method of the aerogel is to use graphene oxide and Fe3O4Taking the raw materials as raw materials, obtaining gel through hydrothermal reaction, magnetizing the gel in a magnetic field, freezing the gel by adopting liquid nitrogen, and drying and shaping the gel to obtain three-dimensional graphene/Fe with an ordered structure3O4In the aerogel, in the ordered three-dimensional aerogel system of this structure, the conduction channel has been established along magnetic field axial direction to graphite alkene skeleton texture, promotes the conduction of electron, phonon etc. along this direction. The invention solves the problems of high disorder degree, irregular dispersion, low conduction efficiency and the like of a three-dimensional graphene aerogel system.
Description
Technical Field
The invention relates to the technical field of aerogel production, in particular to graphene/Fe with an ordered structure3O4A preparation method of aerogel.
Background
graphene/Fe3O4The material is used as a novel magnetic catalytic material, and has the characteristics of environmental friendliness, reusability and the like. But at present graphene/Fe3O4Most of aerogel materials are isotropic and disordered in structure; or magnetic Fe3O4The particles are uniformly oriented and distributed under the action of a magnetic field, and the influence on the graphene framework is avoided.
The patent CN102553593B by He Guang Yu of Changzhou university discloses a preparation method of a magnetic nano ferroferric oxide-graphene composite catalyst, which is obtained by reacting graphite oxide with iron salt at 50-90 ℃ and adding ammonia water to adjust the pH value to 9-11, carrying out magnetic separation on the product, washing with deionized water, and drying. Although the ferroferric oxide-graphene composite material prepared by the method is uniform in particle size and uniform in dispersion, the distribution of a three-dimensional system of the composite material is not uniform.
In order to further simplify the production process, how to adopt graphene oxide and ferroferric oxide as raw materials to prepare the modified graphene material loaded with the ferroferric oxide, which is directionally arranged in the axial direction and has an ordered structure, is the direction of the research of the subject group all the time.
Disclosure of Invention
The invention aims to provide the graphene/Fe with the ordered structure3O4The preparation method of the aerogel is to use graphene oxide and Fe3O4Taking the raw materials as raw materials, obtaining gel through hydrothermal reaction, magnetizing the gel in a magnetic field, freezing the gel by adopting liquid nitrogen, and drying and shaping the gel to obtain graphene/Fe with an ordered structure3O4An aerogel.
graphene/Fe with ordered structure3O4A method for preparing an aerogel comprising the steps of:
(1) weighing graphene oxide and Fe with the weight ratio of 0.5-1.5: 13O4A nanopowder;
(2) weighing the graphene oxide and Fe3O4The nano powder is reacted by a hydrothermal method to prepare graphene/Fe3O4Gelling;
(3) preparing the graphene/Fe prepared in the step (2)3O4The gel is washed for a plurality of times by deionized water until the washed deionized water is neutral;
(4) washing the graphene/Fe3O4The gel is placed in a magnetic field with the strength of 500-5000 Oe for magnetization to form three-dimensional ordered graphene/Fe3O4Gelling;
(5) taking out three-dimensional ordered graphene/Fe from a magnetic field3O4Immediately placing the gel in liquid nitrogen for freeze shaping, and then placing the sample in a freeze dryer for further dehydration and drying to obtain the stable graphene/Fe with ordered structure3O4An aerogel.
Preferably, Fe described in step (1)3O4The particle size of the nanometer powder is 1-20 nm.
Preferably, the temperature of the hydrothermal reaction in the step (2) is 200-350 ℃, and the reaction time is 2-5 h.
Preferably, the magnetization time in the step (4) is 10-30 min.
Preferably, the freeze-setting time of the step (5) in liquid nitrogen is 1-2h, and the drying time in a freeze dryer is 24-48 h.
Compared with the prior art, the invention has the following beneficial effects: the invention prepares graphene/Fe with ordered structure in a magnetic field induced orientation mode3O4An aerogel. Graphene and magnetic nano-ion Fe in hydrothermal process3O4Form a certain interaction force among the Fe and the Fe under the action of a magnetic field3O4The movement of the graphene sheet layer can be driven in the particle movement process, so that the whole three-dimensional system is oriented and arranged along the axial direction of the magnetic field, and graphene/Fe with an ordered structure is obtained3O4An aerogel. The graphene skeleton structure in the three-dimensional aerogel system with the ordered structure constructs a conduction channel along the axial direction of a magnetic field, and promotes the conduction of electrons, phonons and the like along the direction. The invention solves the problems of high disorder degree, irregular dispersion, low conduction efficiency and the like of a three-dimensional graphene aerogel system.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a TEM of graphene oxide in an embodiment of the present invention;
FIG. 2 is an SEM of graphene oxide in an embodiment of the invention;
FIG. 3 shows graphene/Fe prepared in example 1 of the present invention3O4SEM of aerogel;
FIG. 4 shows graphene/Fe prepared in example 1 of the present invention3O4SEM of aerogel;
FIG. 5 shows graphene oxide and Fe in example 1 of the present invention3O4And graphene/Fe3O4XRD of the aerogel;
FIG. 6 shows the graphene/Fe prepared in example 1 of the present invention3O4Compression resilience of the aerogel in the axial and longitudinal directions.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1
(1) 20mg of graphene oxide (TEM and SEM images are shown in FIGS. 1 and 2) and 23.2mg of Fe3O4Uniformly mixing the nano particles under the action of ultrasound, and preparing graphene/Fe by adopting a hydrothermal method3O4The temperature of the hydro-gel hydrothermal reaction is 250 ℃, and the reaction time is 3 h.
(2) graphene/Fe with ordered structure3O4Preparing aerogel:
and taking out the sample obtained by the reaction, and adding a large amount of deionized water for soaking to wash away the monomers which do not participate in the reaction until the deionized water is neutral. Mixing the graphene/Fe3O4The hydrogel is placed in a magnetic field with the strength of 2000 Oe, so that the magnetic nanoparticles are oriented for 20min under the action of the magnetic field, and simultaneously, graphene is driven to be oriented and arranged to form three-dimensional graphene/Fe with an ordered structure3O4A hydrogel. Quickly placing the oriented material in liquid nitrogen for freezing and shaping for 1.5h, and further dehydrating and drying the sample in a freeze dryer for 48h to obtain the graphene/Fe with an ordered structure3O4The aerogels, SEM at different magnifications are shown in figures 3 and 4.
As can be seen from FIG. 3, the prepared graphene/Fe3O4In the aerogel, nano Fe is uniformly loaded on the surface of graphene3O4Particles, as can be seen in FIG. 4, the graphene/Fe produced3O4In the aerogel, the skeleton of the graphene oxide is regularThe whole ordered structure is arranged. Thus, the graphene/Fe of the invention3O4Aerogel not only surface-loaded nano Fe3O4The particles are uniform and ordered, and the skeleton arrangement of the graphene oxide is regular and ordered.
It can also be seen in the XRD pattern of FIG. 5 that graphene/Fe3O4Characteristic peaks of aerogel curves and Fe3O4The characteristic peaks of the curve (2 theta is 30.1, 35.4, 43.1, 53.4, 57.0 and 62.5 degrees, the characteristic peaks corresponding to (220), (311), (400), (422), (511) and (440) are shown), which proves that Fe is successfully converted into Fe3O4The characteristic peak of graphene oxide (001) loaded on the surface of the graphene material at a position of 2 theta approximately equal to 13.2 degrees is not obvious, but a weak peak appears at a position of 2 theta approximately equal to 23.4 degrees, and the peak is a characteristic diffraction peak of reduced graphene, which indicates that the graphene oxide is reduced into graphene in the reaction process.
FIG. 6 is graphene/Fe3O4Axial and longitudinal compression resilience curves of the aerogel, as can be seen from the figure, graphene/Fe3O4The axial compression strength of the aerogel is obviously superior to the longitudinal compression strength, because the framework structure formed by the graphene sheet layers is in a magnetic field and Fe3O4The magnetic particles are preferentially arranged along the direction of a magnetic field to form three-dimensional graphene/Fe with more regular and ordered structure3O4An aerogel system.
Example 2
(1) 10mg of graphene oxide (TEM and SEM images are shown in FIGS. 1 and 2) was mixed with 20mg of Fe3O4Uniformly mixing the nano particles under the action of ultrasound, and preparing graphene/Fe by adopting a hydrothermal method3O4The temperature of the hydro-gel hydrothermal reaction is 200 ℃, and the reaction time is 5 h.
(2) graphene/Fe with ordered structure3O4Preparing aerogel:
and taking out the sample obtained by the reaction, and adding a large amount of deionized water for soaking to wash away the monomers which do not participate in the reaction until the deionized water is neutral. Mixing the graphene/Fe3O4Hydrogel Placement 500In an Oe-strength magnetic field, the magnetic nanoparticles are oriented for 30min under the action of the magnetic field, and simultaneously, graphene is driven to be oriented and arranged to form three-dimensional graphene/Fe with an ordered structure3O4A hydrogel. Quickly placing the oriented material in liquid nitrogen for freezing and shaping for 2h, and further dehydrating and drying the sample in a freeze dryer for 24h to obtain the graphene/Fe with an ordered structure3O4An aerogel.
Example 3
(1) 20mg of graphene oxide (TEM and SEM images are shown in FIGS. 1 and 2) and 28mg of Fe3O4Uniformly mixing the nano particles under the action of ultrasound, and preparing graphene/Fe by adopting a hydrothermal method3O4The temperature of the hydro-gel hydrothermal reaction is 350 ℃, and the reaction time is 2 h.
(2) graphene/Fe with ordered structure3O4Preparing aerogel:
and taking out the sample obtained by the reaction, and adding a large amount of deionized water for soaking to wash away the monomers which do not participate in the reaction until the deionized water is neutral. Mixing the graphene/Fe3O4The hydrogel is placed in a magnetic field with the strength of 1000 Oe, so that the magnetic nanoparticles are oriented for 15min under the action of the magnetic field, and simultaneously, graphene is driven to be oriented and arranged to form three-dimensional graphene/Fe with an ordered structure3O4A hydrogel. Quickly placing the oriented material in liquid nitrogen for freezing and shaping for 2h, further dehydrating and drying the sample in a freeze dryer for 30h to obtain the graphene/Fe with an ordered structure3O4An aerogel.
Example 4
(1) 30mg of graphene oxide (TEM and SEM images are shown in FIGS. 1 and 2) and 20mg of Fe3O4Uniformly mixing the nano particles under the action of ultrasound, and preparing graphene/Fe by adopting a hydrothermal method3O4The temperature of the hydro-gel hydrothermal reaction is 300 ℃, and the reaction time is 2 h.
(2) graphene/Fe with ordered structure3O4Preparing aerogel:
taking out a sample obtained by the reaction, and then,adding a large amount of deionized water for soaking to wash away unreacted monomers until the deionized water is neutral. Mixing the graphene/Fe3O4The hydrogel is placed in a magnetic field with the strength of 5000 Oe, so that the magnetic nanoparticles are oriented for 20min under the action of the magnetic field, and simultaneously, graphene is driven to be oriented and arranged to form three-dimensional graphene/Fe with an ordered structure3O4A hydrogel. Quickly placing the oriented material in liquid nitrogen for freezing and shaping for 2h, and further dehydrating and drying the sample in a freeze dryer for 48h to obtain the graphene/Fe with an ordered structure3O4An aerogel.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (1)
1. graphene/Fe with ordered structure3O4A method for producing an aerogel, characterized by comprising the steps of;
(1) weighing graphene oxide and Fe with the weight ratio of 0.5-1.5: 13O4Nanopowder of Fe3O4The particle size of the nano powder is 1-20 nm;
(2) weighing the graphene oxide and Fe3O4The nano powder is reacted by a hydrothermal method to prepare graphene/Fe3O4Gelling, wherein the temperature of the hydrothermal reaction is 200-350 ℃, and the reaction time is 2-5 h;
(3) preparing the graphene/Fe prepared in the step (2)3O4The gel is washed for a plurality of times by deionized water until the washed deionized water is neutral;
(4) washing the graphene/Fe3O4The gel is placed in a magnetic field with the strength of 500-50000e for magnetization to form three-dimensional ordered graphene/Fe3O4Gel with a magnetization time of10-30min；
(5) Taking out three-dimensional ordered graphene/Fe from a magnetic field3O4Immediately placing the gel in liquid nitrogen for freeze shaping, and then placing the sample in a freeze dryer for further dehydration and drying to obtain the stable graphene/Fe with ordered structure3O4The aerogel is frozen and shaped in liquid nitrogen for 1-2h, and dried in a freeze dryer for 24-48 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413689A (en) * | 2013-07-19 | 2013-11-27 | 北京科技大学 | Method for preparing graphene aerogel and graphene/ metallic oxide aerogel |
| CN105000886A (en) * | 2015-07-13 | 2015-10-28 | 郑州大学 | Macroscopic three-dimensional ultralight Fe3O4 doped graphene aerogel composite material and preparation method |
| CN109320286A (en) * | 2018-11-14 | 2019-02-12 | 武汉纺织大学 | The magnetic graphite alkenyl aerogel material and preparation method thereof for having ordered structure |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413689A (en) * | 2013-07-19 | 2013-11-27 | 北京科技大学 | Method for preparing graphene aerogel and graphene/ metallic oxide aerogel |
| CN105000886A (en) * | 2015-07-13 | 2015-10-28 | 郑州大学 | Macroscopic three-dimensional ultralight Fe3O4 doped graphene aerogel composite material and preparation method |
| CN109320286A (en) * | 2018-11-14 | 2019-02-12 | 武汉纺织大学 | The magnetic graphite alkenyl aerogel material and preparation method thereof for having ordered structure |
Non-Patent Citations (1)
| Title |
|---|
| Fe3O4 nanoparticle/graphene aerogel composite with enhanced lithium storage performance;Yu Wang et al.;《Applied Surface Science》;20180720;第458卷;第1035-1042页 * |
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