CN113559913B - Sandwich-structured coated nitrogen-doped graphene composite material and preparation method and application thereof - Google Patents
Sandwich-structured coated nitrogen-doped graphene composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000011787 zinc oxide Substances 0.000 claims abstract description 52
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000013067 intermediate product Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000012467 final product Substances 0.000 claims abstract description 4
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- 238000001914 filtration Methods 0.000 claims abstract 2
- 239000000047 product Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 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
- 230000008569 process Effects 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000004298 light response Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
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- 239000010453 quartz Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 102000019197 Superoxide Dismutase Human genes 0.000 description 1
- 108010012715 Superoxide dismutase Proteins 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/38—Organic compounds containing nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with a sandwich structure, and a preparation method and application thereof, and the preparation method comprises the following steps: (1) Firstly, mixing graphene oxide dispersion liquid with aniline, then adding a small amount of ammonium persulfate aqueous solution, stirring, and then continuously adding zinc acetate dihydrate aqueous solution under the stirring condition to obtain a mixed solution; (2) Carrying out hydrothermal reaction on the mixed solution to obtain an intermediate product; (3) And filtering and drying the intermediate product, and calcining under the protection of nitrogen to obtain a final product. The nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with the sandwich structure and the preparation method and application thereof have the advantages of simple preparation method, low cost, visible light response capability, capability of providing rich active reaction points, and capability of effectively realizing the transmission of photo-generated electrons, and are high-performance photocatalytic materials, excellent catalytic activity and catalytic materials applicable to the field of photocatalysis.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with a sandwich structure, and a preparation method and application thereof.
Background
Zinc oxide is used as a typical II-VI semiconductor material, and has the advantages of direct wide band gap (3.37 eV), high catalytic activity, good chemical stability, excellent oxidizing capability, simple preparation method, diversified morphology, no toxicity, low price and the like at room temperature. The zinc oxide conduction band potential (-0.5 v vs. nhe) is more negative than the oxygen redox potential (-0.33 v s. Nhe), so superoxide dismutase can generate negative ion radicals; the valence band potential (2.7 v vs. nhe) is higher than the redox potential of water (2.53 v vs. nhe) so that water molecules can be oxidized by holes to form hydroxyl radicals. The participation of the reaction free radicals effectively improves the photocatalysis reaction of organic pollutants. Research shows that the zinc oxide photocatalytic material is widely applied to degradation of a large amount of organic pollutants, wherein the organic pollutants comprise benzene, xylene, phenol, formaldehyde and the like in water, air and soil, so that the zinc oxide photocatalytic material has great commercial value and application prospect in the fields of environmental protection and the like. However, zinc oxide has a relatively wide band gap and can only absorb ultraviolet light in the solar spectrum, while ultraviolet light only accounts for 3% of the solar spectrum, so that the solar energy utilization rate is low. In addition, the zinc oxide has high photo-generated electron-hole recombination probability, the highest quantum efficiency is only 20 percent, and the photocatalytic activity is low.
Graphene has a high specific surface area and good conductivity, can effectively load catalytic particles and promote the transmission of photo-generated electrons in the field of photocatalysis, reduces the recombination of photo-generated electrons and holes, and is widely researched at present. However, due to the action of Van der Waals force, the aggregation of graphene is serious, which affects the exertion of catalytic performance. Therefore, the development of a novel zinc oxide/graphene composite material and the application of the novel zinc oxide/graphene composite material in the field of photocatalysis have important significance.
Disclosure of Invention
The invention aims to provide a nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with a sandwich structure, and a preparation method and application thereof, wherein the preparation method is simple, low in cost and high in photocatalysis efficiency, has visible light response capability, can provide abundant active reaction points, can effectively realize the transmission of photo-generated electrons, and is a high-performance photocatalysis material.
In order to achieve the above purpose, the invention provides a nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with a sandwich structure, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Firstly, mixing graphene oxide dispersion liquid with aniline, then adding a small amount of ammonium persulfate aqueous solution, stirring, and then continuously adding zinc acetate dihydrate aqueous solution under the stirring condition to obtain a mixed solution; the surface of the graphene oxide contains rich groups, the graphene oxide can be uniformly dispersed in an aqueous solution, aniline is adsorbed on the surface of the graphene oxide due to pi-pi action of the graphene oxide and the aniline after the aniline is added, an aniline oligomer is generated after ammonium persulfate is added, the aniline oligomer can effectively isolate the graphene oxide, the aggregation of the graphene oxide is prevented, and zinc ions are complexed with the aniline oligomer after zinc acetate dihydrate is added, so that the uniform distribution of nano zinc oxide is ensured; the aniline oligomer is used as a nitrogen source and doped in graphene oxide and zinc oxide through chemical bonding; the nitrogen atom doped zinc oxide can change the forbidden bandwidth of the zinc oxide, the photoresponse range of the zinc oxide is expanded to a visible light region, and in addition, the nitrogen doped graphene can improve the electron transmission effect; the material can effectively realize electron transmission in the catalytic reaction process, and can obtain high photocatalytic efficiency;
(2) Carrying out hydrothermal reaction on the mixed solution to obtain an intermediate product; zinc acetate adsorbed on the surface of the aniline oligomer is further pyrolyzed into zinc oxide through hydrothermal reaction, so that the effect of densely and uniformly distributing nano zinc oxide is achieved;
(3) The intermediate product is filtered and dried, and then calcined under the protection of nitrogen to obtain a final product, wherein the final product is a nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with a sandwich structure; the crystal form of zinc oxide and the thermal reduction graphene oxide are further changed into graphene through high-temperature calcination.
Preferably, in the step (1), the concentration of the graphene dispersion liquid is 1-4 mg/mL.
Preferably, in the step (1), the mass ratio of the graphene oxide, the aniline, the ammonium persulfate and the zinc acetate dihydrate is (5-20): 100-500): 10-50: (1000-2000); the mass of the aniline is 8-10 times that of the ammonium persulfate, so that an aniline oligomer is formed.
Preferably, in the step (1), the aqueous ammonium persulfate solution is added and stirred for 1 to 3 hours.
Preferably, in the step (2), the temperature of the hydrothermal reaction is 120-180 ℃ and the reaction time is 8-12 hours.
Preferably, in the step (3), the calcining temperature is 500-700 ℃ and the heat preservation time is 0.5-2 hours.
A nitrogen-doped zinc oxide-coated nitrogen-doped graphene composite material of a sandwich structure, obtained by the preparation method of any one of claims 1-6.
The application of the nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with the sandwich structure is used as a photocatalysis material.
The invention has the beneficial effects that:
1) According to the nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with the sandwich structure, graphene oxide is taken as a framework, an aniline oligomer is taken as an intermediate, and the obtained product has good graphene dispersibility and is densely and uniformly distributed with nano zinc oxide particles on the surface.
2) According to the nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with the sandwich structure, the light response range of the nitrogen-doped zinc oxide is expanded to a visible light region, the nitrogen-doped graphene has good electron transmission capability, and meanwhile, due to the fact that active points are densely, uniformly and abundantly distributed on the surface, excellent photocatalytic performance can be obtained.
3) The preparation method of the nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material is simple to operate and low in cost, and can be popularized to the preparation of other metal oxide/graphene composite materials with sandwich structures.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
Fig. 1 is an SEM of nitrogen-doped zinc oxide coated nitrogen-doped graphene of a sandwich structure prepared in example 1 of the present invention.
Fig. 2 is a TEM of nitrogen-doped zinc oxide coated nitrogen-doped graphene of the sandwich structure prepared in example 1 of the present invention.
Fig. 3 is a schematic diagram of nitrogen-doped zinc oxide coated nitrogen-doped graphene prepared by the method for preparing the sandwich structure.
Fig. 4 is an XPS diagram of nitrogen-doped zinc oxide coated nitrogen-doped graphene prepared by the present invention in a sandwich structure.
Fig. 5 is an SEM image of graphene/zinc oxide material prepared in example 2 of the present invention.
Fig. 6 shows the degradation of methyl orange by graphene, the product of example 1, and the product of example 2 under simulated sunlight.
Detailed Description
The present invention will be further described with reference to examples in which various chemicals and reagents are commercially available unless otherwise specified.
Examples
Adding 30mL of deionized water into 10mL of graphene oxide dispersion liquid containing 1mg/mL, adding 0.4mL of aniline, dropwise adding 2mL of aqueous solution containing 20mg/mL of ammonium persulfate, stirring at a high speed, dissolving 1.5 g of zinc acetate dihydrate into 20mL of deionized water, adding into the mixed solution, stirring for 2.5 hours, transferring into a hydrothermal reaction kettle, maintaining the temperature at 160 ℃, reacting for 12 hours, naturally cooling, and performing suction filtration and drying. The obtained solid was placed in a quartz crucible, heated to 600 ℃ at 5 ℃/min under nitrogen atmosphere, and naturally cooled after heat preservation for 30 minutes. As can be seen from fig. 1 and fig. 2, the target product is flaky graphene, and a large number of zinc oxide nanoparticles are densely and uniformly distributed on the upper surface and the lower surface, so that the zinc oxide coated graphene composite material with the sandwich structure is formed. As can be seen from fig. 3, the target product is composed of carbon, zinc, oxygen, and nitrogen elements, indicating that the nitrogen elements are doped into zinc oxide and graphene.
Comparative example
The preparation process of the graphene/zinc oxide composite is similar to that of the embodiment 1, and is mainly used for examining the influence of the aniline oligomer on the nitrogen-doped graphene/nitrogen-doped zinc oxide sandwich structure composite, so that aniline and ammonium persulfate are not added in the preparation process. The specific process is as follows:
10mL of graphene oxide dispersion liquid containing 1mg/mL is taken and added with 30mL of deionized water, after high-speed stirring, 1.5 g of zinc acetate dihydrate is dissolved into 20mL of deionized water and added into the mixed solution, after stirring for 2.5 hours, the mixture is transferred into a hydrothermal reaction kettle, kept at 160 ℃ for 12 hours, and after reaction, the mixture is naturally cooled, filtered and dried. The obtained solid was placed in a quartz crucible, heated to 600 ℃ at 5 ℃/min under nitrogen atmosphere, and naturally cooled after heat preservation for 30 minutes. As can be seen from fig. 5, the graphene in the target product has a significant agglomeration phenomenon.
Test experiment
The prepared methyl orange solution was degraded under simulated solar conditions using graphene, comparative examples and examples.
Fig. 6 is a graph of degradation conditions of graphene, graphene/zinc oxide, and nitrogen-doped zinc oxide/nitrogen-doped graphene on methyl orange under simulated sunlight in the examples, and fig. 6 shows that the graph of fig. 6 shows that the nitrogen-doped zinc oxide/nitrogen-doped graphene shows the most excellent photocatalytic effect after 80min, so that the methyl orange in the solution is degraded by 81%.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (7)
1. The preparation method of the nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with the sandwich structure is characterized by comprising the following steps of:
(1) Firstly, mixing graphene oxide dispersion liquid with aniline, then adding a small amount of ammonium persulfate aqueous solution, stirring, and then continuously adding zinc acetate dihydrate aqueous solution under the stirring condition to obtain a mixed solution; the mass ratio of the graphene oxide to the aniline to the ammonium persulfate to the zinc acetate dihydrate is (5-20): 100-500): 10-50: (1000-2000);
(2) Carrying out hydrothermal reaction on the mixed solution to obtain an intermediate product;
(3) And filtering and drying the intermediate product, calcining under the protection of nitrogen to obtain a final product, wherein the product is a flaky graphene, the upper and lower surfaces of the graphene are densely and uniformly distributed with a large number of zinc oxide nano particles, the product consists of carbon, zinc, oxygen and nitrogen elements, the nitrogen elements are doped into the zinc oxide and the graphene, and finally the nitrogen-doped zinc oxide-coated nitrogen-doped graphene composite material with a flaky sandwich structure is formed.
2. The preparation method of the nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with the sandwich structure as claimed in claim 1, which is characterized by comprising the following steps: in the step (1), the concentration of the graphene dispersion liquid is 1-4 mg/mL.
3. The preparation method of the nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with the sandwich structure as claimed in claim 1, which is characterized by comprising the following steps: in the step (1), a small amount of the ammonium persulfate aqueous solution is added and stirred for 1 to 3 hours.
4. The preparation method of the nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with the sandwich structure as claimed in claim 1, which is characterized by comprising the following steps: in the step (2), the temperature of the hydrothermal reaction is 120-180 ℃ and the reaction time is 8-12 hours.
5. The preparation method of the nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with the sandwich structure as claimed in claim 1, which is characterized by comprising the following steps: in the step (3), the calcining temperature is 500-700 ℃ and the heat preservation time is 0.5-2 hours.
6. The sandwich structured nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material of claim 1, wherein the composite material is characterized by: obtained by the process according to any one of claims 1 to 5.
7. The application of the nitrogen-doped zinc oxide coated nitrogen-doped graphene composite material with the sandwich structure as claimed in claim 6, which is characterized in that: as a photocatalytic material.
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CN110479342A (en) * | 2019-08-09 | 2019-11-22 | 上海应用技术大学 | A kind of monatomic catalyst of cuprum nickle duplex metal of N-rGO load and its preparation and application |
CN112626868A (en) * | 2020-12-17 | 2021-04-09 | 安徽工程大学 | Efficient photocatalytic flexible composite fiber membrane and preparation method thereof |
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