CN111039283A - Microwave-assisted preparation of metal oxide/graphene nano-structure material and preparation method thereof - Google Patents
Microwave-assisted preparation of metal oxide/graphene nano-structure material and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 102
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 56
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 56
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 16
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- 230000000694 effects Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
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- 239000004246 zinc acetate Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
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- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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Abstract
The invention provides a microwave-assisted preparation method of a metal oxide/graphene nano-structure material, wherein the nano-structure material takes a reduced graphene oxide nano-sheet as a matrix, a second-phase metal oxide is loaded on the reduced graphene oxide nano-sheet, and the second-phase metal oxide is In2O3、Fe2O3、Co3O4And one or more of ZnO and the second-phase metal oxide is in a granular or cluster shape with the size of 3-50 nm on the reduced graphene oxide nano sheet. According to the invention, reduced graphene oxide is used as a matrix to load second-phase metal oxide particles or strip clusters, and the introduction of nano particles or strip clusters plays a role in supporting graphene in a space blocking manner, so that stacking and curling of graphene sheet layers are greatly reduced, and agglomeration of the second-phase metal oxide particles is prevented, thereby obtaining a larger specific surface area and improving various related performances such as gas sensitivity.
Description
Technical Field
The invention relates to the technical field of material synthesis, in particular to a microwave-assisted preparation method of a metal oxide/graphene nano-structure material and a preparation method thereof.
Background
The metal oxide semiconductor is widely applied to the fields of gas sensitivity, photocatalysis, electrocatalysis and the like due to the unique photoelectric characteristics of the metal oxide semiconductor. Among them, metal oxide sensors are receiving particular attention in gas detection due to their low-cost and highly easy-to-use manufacturing process. However, the metal oxide semiconductor nano material with a single structure often has the defects of easy agglomeration, low specific surface and the like, and the specific surface needs to be improved by constructing the nano composite material with a multilevel structure so as to improve various related performances. By introducing some low-dimensional nanostructures such as nanowires, nanotubes, nanoplates, and the like, novel multi-stage composites can be prepared to overcome the aggregation of metal oxide nano-sized particles. The graphene has a unique two-dimensional structure, so that the requirement can be effectively met, and meanwhile, the perfect quantum tunneling effect, the half-integer quantum Hall effect, the never-disappearing conductivity and other special properties of the graphene are beneficial to improving various performances of the composite material, for example, the detection sensitivity is expected to be improved and the gas-sensitive detection temperature is expected to be reduced in the gas-sensitive detection aspect.
The graphene has an extremely large theoretical specific surface area of about 2630 m2g-1However, due to the ultra-thin characteristic of graphene, graphene is easy to stack and agglomerate, and is often stored in the form of derivative graphene oxide. The graphene oxide has a plurality of oxygen-containing functional groups on the surface, and the graphene oxide is used as a substrate to facilitate the nucleation and growth of metal oxide nanoparticles on the surface, and the nanoparticlesAnd the graphene is introduced to play a role in space blocking, so that stacking and curling among graphene sheet layers are greatly reduced. The synthesis method and process are key to realizing ideal material structure, and how to realize uniform distribution of the second phase in the preparation process of the nano composite material is the main problem in the synthesis control of the nano composite material. Hydrothermal method, high temperature reflux method, electrostatic spinning technology and the like are reported to be used for preparing the metal oxide/graphene nano composite material. These processes generally require higher temperatures and longer times during the reaction, and the second phase is more difficult to control uniformly and still has a large amount of agglomeration. In order to obtain a novel adjustable metal oxide/graphene nanocomposite material to improve various performances, a green and efficient preparation process is still under deep research. The microwave-assisted method for preparing the metal oxide/graphene nano structure has wide application prospect due to rapid dynamics, greenness and energy conservation.
Disclosure of Invention
The invention provides a microwave-assisted preparation method of a metal oxide/graphene nano-structure material, and provides a method for preparing a metal oxide/graphene nano-structure product with controllable appearance and particle size of second-phase particles and uniform distribution by microwave assistance under normal pressure. The method takes soluble metal acetate, nitrate and the like and graphene oxide as precursors, and adopts a microwave-assisted simple precipitation method to prepare the product under normal atmospheric pressure and relatively low temperature.
The technical scheme for realizing the invention is as follows:
the microwave-assisted preparation of the metal oxide/graphene nano-structure material takes reduced graphene oxide nano-sheets as a matrix, and second-phase metal oxide is loaded on the reduced graphene oxide nano-sheets and is In2O3、Fe2O3、Co3O4And one or more of ZnO and the second-phase metal oxide is in a granular or cluster shape with the size of 3-50 nm on the reduced graphene oxide nano sheet.
When the second phase metal oxide is In2O3In is obtained2O3Graphene multi-level structure productSecond phase of In2O3The size of the nano particles is 3-40 nm; when the second-phase metal oxide is Fe2O3Then, Fe is obtained2O3Second-phase Fe on graphene multi-level structure product2O3The size of the nano particles is 4-15 nm; when the second-phase metal oxide is Co3O4Then, Co is obtained3O4Second phase Co on graphene multilevel structure product3O4The size of the nano particles is 10-45 nm; and when the second-phase metal oxide is ZnO, the size of second-phase ZnO nanoparticles on the obtained ZnO/graphene hierarchical structure product is 6-20 nm.
The mass ratio of the second-phase metal oxide to the reduced graphene oxide is 1: (1-12).
The nano-structure material is prepared by using soluble metal salt and graphene oxide as precursors and adopting a normal-pressure microwave-assisted method.
The preparation method for preparing the metal oxide/graphene nano-structure material under the assistance of the microwaves comprises the following steps:
(1) dissolving soluble metal salt in a graphene oxide solution, and stirring for 0.5-2 h to form a uniform suspension;
(2) performing irradiation reaction on the suspension in the step (1) in a microwave oven, naturally cooling to room temperature, collecting precipitates through centrifugal separation, and washing the precipitates for 3-6 times by using deionized water to obtain a washing product; the graphene oxide nanosheet is synthesized by adopting an improved hummer's method;
(3) freeze-drying the washing product in the step (2) to obtain an intermediate; and (3) calcining the intermediate in vacuum to obtain the metal oxide/graphene nano-structure material.
In the step (1), the soluble metal salt is a salt corresponding to a second-phase metal oxide, and the mass ratio of the soluble metal salt to the graphene oxide nanosheet is 1: (0.1 to 18).
The microwave frequency of the microwave oven in the step (2) is 2450MHz or 915 MHz, the microwave power is 100-1000W, and the irradiation reaction is carried out for 1-20 min.
The temperature of the freeze drying in the step (3) is-10 to-80 ℃, and the time is 1 to 12 hours.
And (4) in the step (3), the vacuum calcination temperature is 300-700 ℃, and the time is 0.5-5 h.
Dissolving soluble metal salt and urea in a graphene oxide solution, and stirring to form a uniform suspension, wherein the molar ratio of the urea to the soluble metal salt is (0-6): 1.
the invention has the beneficial effects that:
according to the metal oxide/graphene nano-structure product, reduced graphene oxide is used as a substrate to load second-phase metal oxide particles or strip clusters, and the introduction of the nano-particles or strip clusters plays a role in supporting space blocking of graphene, so that stacking and curling of graphene sheet layers are greatly reduced, and meanwhile, agglomeration of the second-phase metal oxide particles is prevented, and thus a larger specific surface area is obtained, and various related performances such as gas sensitivity are improved; the preparation method is safe, simple, green and energy-saving; the second phase metal oxide has regular particle appearance, easily controlled particle size uniformity and good large-scale repeatability.
As one of carbon materials, graphene oxide has excellent wave-absorbing performance, microwave heating belongs to typical body heating, graphene oxide becomes a hot spot relative to the surrounding environment under microwave irradiation, and the graphene oxide is favorable for nucleation growth of metal oxide nanoparticles on the surface of the graphene oxide under the assistance of microwaves due to the fact that a plurality of oxygen-containing functional groups are arranged on the surface of the graphene oxide. The method can realize the rapid, energy-saving and high-efficiency preparation of the metal oxide by means of microwave-assisted synthesis of unique thermal effect and non-thermal effect, and the shape and the particle size of the second-phase metal oxide particles are uniform and controllable.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows In example 12O3Digital photos of graphene nanostructure products;
FIG. 2 shows the precursor graphene oxide and In example 12O3An X-ray diffraction pattern of the graphene nanostructure product;
FIG. 3 shows graphene oxide and In example 12O3Scanning electron microscope photographs of graphene nanostructure products;
FIG. 4 shows In example 12O3Transmission electron microscope and high resolution transmission photograph of graphene nano-structured products;
FIG. 5 shows In example 12O3The gas-sensitive response curve of the graphene nano-structure product to NO gas.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Normal pressure microwave assisted In preparation2O3Graphene nanostructured products:
0.4 g of In (NO) is weighed out3)3·4.5H2O was dissolved in 50 mL of 0.5 g/L graphene oxide suspension, 0.25 g urea was added with stirring, and stirring was continued in an Erlenmeyer flask for 30 minutes to form a uniform mixed solution. Then, the mixed solution is irradiated in a microwave oven for reaction for about 4 minutes, wherein the microwave frequency is 2450 Hz, and the power is 500W. After naturally cooling to room temperature, the black precipitate was collected by centrifugation and washed 4 times with deionized water. Freeze drying at-60 deg.C for 8 hr, collecting powder sample, and vacuum calcining at 550 deg.C for 2 hr to obtain In2O3Reducing a graphene oxide product, wherein the mass ratio of indium nitrate to graphene oxide is 16: 1.
the resulting sample was in the form of a black floe powder, as shown in the digital photograph of fig. 1.
FIG. 2 is an XRD pattern of the obtained sample, and it can be seen that the main phase composition of the sample is cubic In2O3(JCPDS # 06-0416) at 2 θ =10.9oNo obvious diffraction peak of graphene oxide was found, indicating that graphene oxide was reduced to reduced graphene oxide.
FIGS. 3 and 4 are scanning electron micrographs and transmission electron micrographs of a precursor or sample, In2O3Reduction of second phase In graphene oxide2O3The nano particles are granular and are uniformly distributed on the reduced graphene oxide nano sheet, and the grain size is about 3-40 nm.
To produce In2O3The gas sensor manufactured by reducing the graphene oxide nano-structure product as a gas sensitive material can detect low-concentration Nitric Oxide (NO) gas at the temperature of 50 ℃, and fig. 5 is a gas sensitive response curve of detecting 10 ppm and 25 ppm NO gas at the temperature of 100 ℃, so that the gas sensor has higher sensitivity to the NO gas, and the obtained In is proved2O3The graphene nano-structure product can be used as a low-temperature NO gas detection material with excellent performance.
Example 2
The method for preparing the metal oxide/graphene nano-structure product under the assistance of normal pressure microwaves comprises the following steps:
0.25 g of Fe (NO) was added under magnetic stirring3)3·9H2Sequentially adding O and 0.1 g of urea into 50 mL of 1g/L graphene oxide suspension, and stirring for 1 h to fully dissolve the O and the urea to form uniform mixed liquor; placing the mixed solution in a microwave oven, and reacting for 15 min under microwave with frequency of 2450MHz and power of 600W to fully react; centrifugally separating the reacted precipitate, washing with deionized water for many times, freeze-drying at-20 deg.C for 12 hr, vacuum calcining at 700 deg.C for 2 hr to obtain Fe2O3Reduced graphene oxide product. The mass ratio of the ferric nitrate to the graphene oxide is 5: 1, Fe (NO)3)3The molar ratio to urea was 2.5. The obtained sample is black floating powder and is suitable for low-concentration H2S gasThe high low-temperature detection sensitivity is shown.
Example 3
The method for preparing the metal oxide/graphene nano-structure product under the assistance of normal pressure microwaves comprises the following steps:
respectively adding 0.5 g of C under the condition of magnetic stirring4H6O4Zn·2H2Sequentially adding O and 0.2 g of urea into 50 mL of 1g/L graphene oxide suspension, and stirring for 2 h to fully dissolve the O and the urea to form uniform mixed liquor; placing the mixed solution in a microwave oven, and reacting for 15 minutes under microwave with the frequency of 2450MHz and the power of 600W to fully react; and (3) carrying out centrifugal separation and multiple deionized water washing on the precipitate after reaction, freeze-drying the precipitate at the temperature of-60 ℃ for 12 hours, and then carrying out vacuum calcination at the temperature of 500 ℃ for 3 hours to finally obtain a ZnO/reduced graphene oxide product. The mass ratio of the zinc acetate to the graphene oxide is 10: 1, the molar ratio of the zinc acetate to the urea is 3. The obtained sample is black flotage powder, and shows higher low-temperature detection sensitivity to organic volatile ethanol.
Example 4
The method for preparing the metal oxide/graphene nano-structure product under the assistance of normal pressure microwaves comprises the following steps:
0.12 g of Co (NO) was added under magnetic stirring3)2·6H2Sequentially adding O and 0.1 g of urea into 20 mL of 1g/L graphene oxide suspension, and stirring for 2 h to fully dissolve the O and the urea to form uniform mixed liquor; placing the mixed solution in a microwave oven, and reacting for 20 min under the microwave of 915 MHz frequency and 100W power to fully react; collecting the precipitate by centrifugal separation, and washing the precipitate for 6 times by using deionized water to obtain a washing product; freeze-drying the washed product at-10 deg.C for 12 h to obtain intermediate; then the intermediate is calcined in vacuum for 5h at 300 ℃, and finally Co is obtained3O4A graphene product. The mass ratio of the cobalt oxide to the graphene oxide is 1.6: 1, the molar ratio of the cobalt nitrate to the urea is 0.2. The obtained sample is black powder and shows higher low-temperature detection sensitivity to organic volatile ethanol.
Example 5
The method for preparing the metal oxide/graphene nano-structure product under the assistance of normal pressure microwaves comprises the following steps:
45 mg of Co (CH)3COO)2·4H2Dissolving O in 50 mL of 0.5 g/L graphene oxide suspension, and stirring for 1.5h to form uniform suspension; irradiating the suspension in a microwave oven for 1 min, wherein the microwave frequency of the microwave oven is 2450MHz, and the microwave power is 1000W; naturally cooling to room temperature, collecting precipitate by centrifugal separation, and washing the precipitate with deionized water for 3 times to obtain a washing product; freeze-drying the washed product at-80 deg.C for 1 h to obtain powder sample; calcining the powder sample at 500 ℃ in vacuum for 0.5 h to obtain Co3O4Graphene nanostructured materials. The obtained sample is black powder, and has higher detection sensitivity to organic volatile acetone steam.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A microwave-assisted preparation method of a metal oxide/graphene nano-structured material is characterized by comprising the following steps: the nano-structure material takes reduced graphene oxide nano-sheets as a matrix, and second-phase metal oxide is loaded on the reduced graphene oxide nano-sheets and is In2O3、Fe2O3、Co3O4And one or more of ZnO and the second-phase metal oxide is in a granular or cluster shape with the size of 3-50 nm on the reduced graphene oxide nano sheet.
2. The microwave-assisted preparation of metal oxide/graphene nanostructured material according to claim 1, wherein: the mass ratio of the second-phase metal oxide to the reduced graphene oxide is 1: (1-12).
3. The microwave-assisted preparation of metal oxide/graphene nanostructured material according to claim 1, wherein: the nano-structure material is prepared by using soluble metal salt and graphene oxide as precursors and adopting a normal-pressure microwave-assisted method.
4. The microwave-assisted preparation method of a metal oxide/graphene nanostructured material according to any one of claims 1 to 3, characterized by the following steps:
(1) dissolving soluble metal salt in a graphene oxide solution, and stirring to form a uniform suspension;
(2) performing irradiation reaction on the suspension in the step (1) in a microwave oven, naturally cooling to room temperature, collecting precipitates through centrifugal separation, and washing the precipitates for 3-6 times by using deionized water to obtain a washing product;
(3) freeze-drying the washing product in the step (2) to obtain an intermediate; and (3) calcining the intermediate in vacuum to obtain the metal oxide/graphene nano-structure material.
5. The microwave-assisted preparation method of a metal oxide/graphene nanostructure material according to claim 4, characterized in that: in the step (1), the soluble metal salt is a salt corresponding to the second-phase metal oxide, and the mass ratio of the soluble metal salt to the reduced graphene oxide is 1: (1-12).
6. The microwave-assisted preparation method of a metal oxide/graphene nanostructure material according to claim 4, characterized in that: the microwave frequency of the microwave oven in the step (2) is 2450MHz or 915 MHz, the microwave power is 100-1000W, and the irradiation reaction is carried out for 1-20 min.
7. The microwave-assisted preparation method of a metal oxide/graphene nanostructure material according to claim 4, characterized in that: the temperature of the freeze drying in the step (3) is-10 to-80 ℃, and the time is 1 to 12 hours.
8. The microwave-assisted preparation method of a metal oxide/graphene nanostructure material according to claim 4, characterized in that: and (4) in the step (3), the vacuum calcination temperature is 300-700 ℃, and the time is 0.5-5 h.
9. The method for preparing a metal oxide/graphene nano-structured material with the assistance of microwaves according to any one of claims 5 to 8, wherein: dissolving soluble metal salt and urea in a graphene oxide solution, and stirring to form a uniform suspension, wherein the molar ratio of the urea to the soluble metal salt is (0-6): 1.
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