CN114180680A - Graphite oxide nanoparticle electrode material and preparation method thereof - Google Patents
Graphite oxide nanoparticle electrode material and preparation method thereof Download PDFInfo
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- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 66
- 239000010439 graphite Substances 0.000 title claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000007772 electrode material Substances 0.000 title claims abstract description 35
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 5
- 229910003264 NiFe2O4 Inorganic materials 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000010865 sewage Substances 0.000 abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 238000004043 dyeing Methods 0.000 abstract description 3
- 238000007639 printing Methods 0.000 abstract description 3
- 239000004753 textile Substances 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 19
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 13
- 229940043267 rhodamine b Drugs 0.000 description 13
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910003321 CoFe Inorganic materials 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
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Images
Classifications
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a graphite oxide nanoparticle electrode material and a preparation method thereof, belonging to the technical field of sewage treatment. The inventionThe graphite oxide nano particle electrode material is based on NiFe2O4‑CoFe2O4/TiO2A supported graphite oxide nanoparticle electrode material. The preparation method comprises the following steps: preparation of graphite oxide, NiFe2O4‑CoFe2O4Preparation of the solution, TiO2Preparing sol-gel; finally mixing NiFe2O4‑CoFe2O4Dropwise addition of the solution to TiO2And adding the ground graphite oxide into the sol-gel to obtain the graphite oxide nanoparticle electrode material. The graphite oxide nanoparticle electrode material has a good photoelectric catalytic effect, can effectively degrade organic matters, has a good heavy metal adsorption effect, and can be well applied to the field of wastewater treatment in the printing and dyeing industry, the textile industry and the like.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a graphite oxide nanoparticle electrode material and a preparation method thereof.
Background
With the continuous and deep development of the global industrial and agricultural chemical, the wastewater discharged in the industrial and agricultural production is gradually increased, the wastewater has the characteristics of difficult degradation, high organic matter content, large pH value change and the like, the wastewater is discharged into rivers, lakes and seas without being well treated, and various pollutants contained in the wastewater can seriously affect the ecological environment and cause serious harm to water bodies and even human health.
At present, in the sewage treatment method by using photocatalytic semiconductor material, TiO only2Photocatalytic oxidation techniques still exist: low solar energy utilization rate and high recombination probability of photoproduction electron-hole pairsAnd difficulty in separation and recovery. These problems have limited their use to some extent in the actual treatment of water. Most of the noble metals on the market are TiO2Modified to strengthen the TiO2But the precious metal resources are scarce and the cost is high. Therefore, the research on the graphite oxide nano particle electrode material which has reasonable cost and good photoelectric catalysis effect and can effectively degrade organic matters has very important significance and has very wide application prospect in the aspect of sewage treatment.
Disclosure of Invention
The invention provides a graphite oxide nanoparticle electrode material and a preparation method thereof, and aims to solve the problems of complex preparation process, high metal price, poor wastewater treatment effect and the like of a photocatalyst for treating organic matters in wastewater. The electrode material has a good photoelectrocatalysis effect, can effectively degrade organic matters, has a good heavy metal adsorption effect, and can be well applied to the field of wastewater treatment containing more organic matters, organic dyes and heavy metals in the printing and dyeing industry, the textile industry and the like.
In order to achieve the purpose, the invention provides the following scheme:
one of the purposes of the invention is to provide a graphite oxide nano particle electrode material, and the electrode material is based on NiFe2O4-CoFe2O4/TiO2A supported graphite oxide nanoparticle electrode material.
Further, NiFe in the electrode material2O4-CoFe2O4、TiO2The mass ratio of the graphite oxide to the graphite oxide is (1-2): 1.
The invention also aims to provide a preparation method of the graphite oxide nano particle electrode material, which comprises the following steps:
(1) mixing graphite oxide and hydrazine hydrate, adjusting the pH value of the solution to be alkaline, freezing, drying and grinding for later use;
(2)NiFe2O4-CoFe2O4preparation of the solution: dissolving cobalt nitrate hexahydrate and ferric nitrate nonahydrate in anhydrous ethanol, and adding waterSealing and stirring to obtain a dark red transparent solution A; dissolving nickel nitrate hexahydrate and ferric nitrate nonahydrate in absolute ethyl alcohol, adding water, and sealing and stirring to obtain a light red transparent solution B; dripping the solution A into the solution B, sealing and stirring to prepare NiFe2O4-CoFe2O4A solution;
(3)TiO2preparation of sol-gel: mixing absolute ethyl alcohol and tetrabutyl titanate, adding glacial acetic acid and dilute nitric acid, sealing and stirring to form TiO2Sol-gel;
(4) mixing NiFe2O4-CoFe2O4Dropwise addition of the solution to TiO2And adding the ground graphite oxide into the sol-gel, stirring for 1h, filtering and drying to obtain the graphite oxide nanoparticle electrode material.
Further, the preparation steps of the graphite oxide are as follows:
a. and (3) a low-temperature reaction stage: adding natural crystalline flake graphite (500 meshes) into concentrated sulfuric acid (98%), wherein the concentrated sulfuric acid is 1g and 28mL, and reacting in an ice-water bath for 5h (0 ℃);
b. a medium-temperature reaction stage: KMnO is added in two times4Graphite KMnO4(m/m) ═ 1:3.5, 1h at intervals, 70% of the total mass were added for the first time, and stirring was carried out overnight; the remaining 30% of KMnO was added a second time4Heating to 40 ℃, continuing to react for 5h, and then adding ultrapure water and KMnO4336mL of ultrapure water (14 g).
c. A high-temperature reaction stage: heating to 90 ℃, reacting the solution to be golden yellow, stopping heating when the reaction solution reacts for 15-30 minutes and tends to become deep, and adding H2O2And (3) pumping out the hot water of the mixed water bath until no bubbles appear, changing the hot water into normal-temperature water, stopping the reaction after continuously stirring for 30 minutes, continuously adding pure water, standing and removing supernate. Washing with dilute hydrochloric acid for 3 times, stirring and standing, removing supernatant, repeating the operation for 3 times, removing the supernatant to obtain a precipitate, washing with pure water, and centrifuging for 2-3 times until the pH of the supernatant is 3.
d. Mixing the graphite oxide and the hydrazine hydrate according to the mass ratio of 10 to (8-9), adjusting the pH value of the solution to 8, stirring the solution for 80min at 100 ℃, freezing the solution for 12h, drying the solution for 24h, grinding the dried solution and storing the ground solution in the dark.
Further, in the step (2), the cobalt nitrate hexahydrate and the iron nitrate nonahydrate are CoFe2O4Weighing the Co to Fe with the medium atomic ratio of 1 to 2; the mass-volume ratio of the cobalt nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL to 3 mL.
Further, in the step (2), the nickel nitrate hexahydrate and the ferric nitrate nonahydrate are NiFe2O4Weighing Ni and Fe in the ratio of 1: 2; the mass-volume ratio of the nickel nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL to 3 mL.
Further, in the step (3), the volume ratio of the absolute ethyl alcohol to the tetrabutyl titanate is 1 (1-2).
Further, in the step (3), the volume ratio of the absolute ethyl alcohol to the glacial acetic acid to the dilute nitric acid is 10:3:10, and the concentration of the dilute nitric acid is 1 mol/L.
Further, the sealing stirring is carried out for 1h at 40 ℃ on a constant-temperature magnetic stirrer.
Further, in the step (4), the drying is carried out for 24 hours at 120-160 ℃.
The invention discloses the following technical effects:
the preparation method of the graphite oxide nanoparticle electrode material is simple, and the raw materials are cheap and easily available and have wide sources; NiFe with Ni and Co as compound2O4、CoFe2O4Has high catalytic activity and material stability in non-platinum-based transition metal compounds, and NiFe2O4-CoFe2O4Fe in (1)2+Can be reacted with H2O2The reaction generates active substance OH with strong oxidizing property to degrade organic matters, and Fe is generated at the same time3+Coagulating sedimentation reaction is carried out to remove partial organic matters. Easy TiO loading in graphite oxide2Not only can broaden the response range of visible light, but also can effectively separate photoproduction electrons and holes and improve TiO2The adsorption performance of (3). Thus, NiFe2O4-CoFe2O4/TiO2The nano particle electrode material loaded on the graphene oxide has a high sewage treatment application prospect.
The graphite oxide nanoparticle electrode material has a good photoelectric catalysis effect, and can effectively degrade organic matters, such as: rhodamine B, malachite green and the like, and can be well applied to the fields of treatment of wastewater containing more organic matters, organic dyes and heavy metals in the printing and dyeing industry, the textile industry and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed 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 creative efforts.
FIG. 1 is an SEM image of pure, unsupported graphite oxide;
FIG. 2 is an SEM image of the graphite oxide nanoparticle electrode material of example 1;
FIG. 3 shows the effect of different nanoparticle electrodes on the degradation rate of rhodamine B solution;
figure 4 is a graph of the fitted kinetics of different nanoparticle electrodes.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
In the following examples, the specific preparation steps of graphite oxide are as follows:
a. and (3) a low-temperature reaction stage: adding natural crystalline flake graphite (500 meshes) into concentrated sulfuric acid (98%), wherein the concentrated sulfuric acid is 1g and 28mL, and reacting in an ice-water bath for 5h (0 ℃);
b. a medium-temperature reaction stage: KMnO is added in two times4Graphite KMnO4(m/m) ═ 1:3.5, 1h at intervals, 70% of the total mass were added for the first time, and stirring was carried out overnight; the remaining 30% of KMnO was added a second time4Heating to 40 ℃, continuing to react for 5h, and then adding ultrapure water and KMnO4336mL of ultrapure water (14 g).
c. A high-temperature reaction stage: heating to 90 deg.C, reacting for 30 min until the reaction solution turns golden yellow, stopping heating, and adding H2O2Until no air bubble appears, the hot water in the mixed water bath is pumped out and replaced by water at normal temperature (25 ℃), the reaction is stopped after the reaction is continued to be stirred for 30 minutes, and then the reaction is continuedAdding pure water, standing, and removing supernatant. Washing with dilute hydrochloric acid for 3 times, stirring, standing, removing supernatant, repeating the operation for 3 times, removing supernatant to obtain precipitate, washing with pure water, centrifuging for 3 times until the pH of supernatant is 3, separating, and drying to obtain graphite oxide.
Example 1
(1) Mixing graphite oxide and hydrazine hydrate according to the mass ratio of 10:8, adjusting the pH of the solution to 8, freezing, drying and grinding for later use;
(2)NiFe2O4-CoFe2O4preparation of the solution: according to CoFe2O4Weighing cobalt nitrate hexahydrate and ferric nitrate nonahydrate according to the medium atomic ratio Co to Fe being 1:2, dissolving the cobalt nitrate hexahydrate and the ferric nitrate nonahydrate in absolute ethyl alcohol, adding water, wherein the mass-volume ratio of the cobalt nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL to 3mL, and stirring the mixture for 1h at the temperature of 40 ℃ on a constant-temperature magnetic stirrer to obtain a solution A; according to NiFe2O4Weighing nickel nitrate hexahydrate and ferric nitrate nonahydrate according to the proportion of Ni to Fe of 1:2, dissolving in absolute ethyl alcohol, adding water, wherein the mass-volume ratio of the nickel nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL to 3mL, and stirring for 1h at 40 ℃ on a constant-temperature magnetic stirrer to obtain a solution B; dripping the solution A into the solution B, and stirring for 1h at the temperature of 40 ℃ on a constant-temperature magnetic stirrer to prepare NiFe2O4-CoFe2O4A solution;
(3)TiO2preparation of sol-gel: mixing absolute ethyl alcohol and tetrabutyl titanate according to the volume ratio of 1:1, adding glacial acetic acid and dilute nitric acid (1mol/L), wherein the volume ratio of the absolute ethyl alcohol to the glacial acetic acid to the dilute nitric acid is 10:3:10, and stirring for 1h at 40 ℃ on a constant-temperature magnetic stirrer to form TiO2Sol-gel;
(4) mixing NiFe2O4-CoFe2O4Dropwise addition of the solution to TiO2Adding ground graphite oxide, NiFe into sol-gel2O4-CoFe2O4、TiO2And the graphite oxide is stirred and filtered according to the mass ratio of 1:2:1, and the graphite oxide nano particle electrode material is obtained after drying for 24 hours at the temperature of 150 ℃.
Fig. 1 is an SEM image of unsupported graphite oxide. FIG. 2 is an SEM image of the graphite oxide nanoparticle electrode material of this example, and it can be seen from FIG. 2 that NiFe prepared from the material is comparable to the graphite oxide nanoparticle electrode material prepared by the conventional co-precipitation method2O4-CoFe2O4/TiO2The particles are dispersed, so that the particles are not easy to agglomerate seriously, and are loaded on the graphite oxide, so that large pores are generated after sintering, and the specific surface area of the graphite oxide nanoparticle electrode material is increased.
The initial rhodamine B concentration is set as C0 mg/L and the pH is set as 7, 50mL of rhodamine B solution is filled into a 100mL beaker, and the xenon lamp illumination intensity is 10 mu W/m2Experiments are carried out under the conditions, the influence of the electrodes in example 1 and other particles on the rate of degrading rhodamine B through photoelectrocatalysis is examined, and the result is shown in figure 2.
As can be seen from FIG. 3, pure TiO was adsorbed after the dark reaction2Has almost no adsorption capacity to rhodamine B, and is doped with NiFe2O4-CoFe2O4Of TiO 22Has certain adsorption to rhodamine B. Doped with NiFe2O4-CoFe2O4Of TiO 22The capability of degrading rhodamine B under photocatalysis is obviously stronger than that of pure NiFe2O4Or CoFe2O4And the degradation rate of rhodamine B in 60min almost reaches 90%. The reason for this is with NiFe2O4-CoFe2O4With TiO2The capability of photogenerated holes and electron pairs generated by the light source to excite the composite material is gradually enhanced, and after the composite graphite oxide is added, more photogenerated and photogenerated holes with high activity are formed, and more effective hydroxyl free radicals OH and superoxide anions O are generated2 -Thereby enhancing the photocatalytic capability of the composite material.
As can be seen from FIG. 4, NiFe2O4-CoFe2O4/TiO2The linear fitting equation of graphite oxide is that y is 0.0479x +0.0026, R2The k value represents the reaction rate constant at 0.9671, the larger the number the faster the reaction. As is evident from the figure, NiFe2O4-CoFe2O4/TiO2The reaction rate of graphite oxide is significantly higher than that of other kinds of materials.
Example 2
The difference from example 1 is that in step (1), graphite oxide and hydrazine hydrate were mixed in a mass ratio of 10: 9.
Example 3
The same as example 1 except that in step (3), anhydrous ethanol and tetrabutyl titanate were mixed in a volume ratio of 1: 2.
Example 4
The difference from example 1 is that in step (4), NiFe2O4-CoFe2O4、TiO2And the mass ratio of the graphite oxide to the graphite oxide is 2:1: 1.
Comparative example 1
The difference from example 1 is that NiFe2O4-CoFe2O4Replacement of solution by CoFe2O4And (3) solution. In step (2), CoFe is prepared2O4Solution: according to CoFe2O4Weighing cobalt nitrate hexahydrate and ferric nitrate nonahydrate according to the medium atomic ratio Co to Fe being 1:2, dissolving the cobalt nitrate hexahydrate and the ferric nitrate nonahydrate in absolute ethyl alcohol, adding water, wherein the mass-volume ratio of the cobalt nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL to 3mL, and stirring the mixture for 1h at the temperature of 40 ℃ on a constant-temperature magnetic stirrer to obtain CoFe2O4And (3) solution. In the step (4), CoFe2O4Dropwise addition of the solution to TiO2Adding ground graphite oxide, CoFe into sol-gel2O4、TiO2And the graphite oxide is stirred and filtered according to the mass ratio of 1:2:1, and the graphite oxide nano particle electrode material is obtained after drying for 24 hours at the temperature of 150 ℃.
Comparative example 2
The difference from example 1 is that graphite oxide was replaced with untreated natural flake graphite.
Detection method
The electrode materials of the examples and the comparative examples are used for degrading rhodamine B, and the specific method is as follows: adding 100mL of rhodamine B solution into a condensation sleeve cupAdding NiFe2O4-CoFe2O4/TiO2The method comprises the following steps of carrying out dark reaction for 1h by using a graphite oxide nanoparticle electrode and a saturated sodium sulfate solution as an electrolyte to achieve adsorption balance, simulating sunlight by using an 800W xenon lamp, irradiating a reactor, regulating voltage by using a constant-current voltage-stabilized power supply, sampling every 10min, centrifuging for 5min at the rotation speed of 8000r/min, taking supernatant, measuring absorbance of the supernatant at the position of which the lambda is 554nm by using a UV-visible spectrophotometer, calculating corresponding concentration according to a standard curve, and calculating the degradation rate.
TABLE 1
Item | 60min rhodamine B degradation Rate (%) |
Example 1 | 90 |
Example 2 | 72 |
Example 3 | 75 |
Example 4 | 87 |
Comparative example 1 | 83 |
Comparative example 2 | 69 |
As can be seen from Table 1, the degradation rate of the graphite oxide nanoparticle electrode material for rhodamine B treatment for 60min can reach 90%. Comparative example 1 doping with CoFe only2O4The absorption performance of electromagnetic waves is poor, the capacity of photogenerated holes and electron pairs generated by exciting the composite material by a light source is relatively weak, the photogenerated holes and the photogenerated holes with high activity are not easy to form, and hydroxyl radical OH and superoxide anion O are not easy to generate2 -Thereby affecting its photocatalytic ability. Comparative example 2, which employs untreated natural flake graphite, has tightly connected lamellae, small pores, and is not easily intercalated with NiFe2O4-CoFe2O4/TiO2Nanoparticle particles, resulting in insufficient specific surface area of the material.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A graphite oxide nanoparticle electrode material is characterized in that the electrode material is based on NiFe2O4-CoFe2O4/TiO2A supported graphite oxide nanoparticle electrode material.
2. The graphite oxide nanoparticle electrode material as claimed in claim 1, wherein NiFe is present in the electrode material2O4-CoFe2O4、TiO2The mass ratio of the graphite oxide to the graphite oxide is (1-2): 1.
3. A method for preparing the graphite oxide nanoparticle electrode material as defined in any one of claims 1 to 2, comprising the steps of:
(1) mixing graphite oxide and hydrazine hydrate, adjusting the pH value of the solution to be alkaline, freezing, drying and grinding for later use;
(2)NiFe2O4-CoFe2O4preparation of the solution: dissolving cobalt nitrate hexahydrate and ferric nitrate nonahydrate in absolute ethyl alcohol, adding water, sealing and stirring to obtain a solution A; dissolving nickel nitrate hexahydrate and ferric nitrate nonahydrate in absolute ethyl alcohol, adding water, sealing and stirring to obtain a solution B; dripping the solution A into the solution B, sealing and stirring to prepare NiFe2O4-CoFe2O4A solution;
(3)TiO2preparation of sol-gel: mixing absolute ethyl alcohol and tetrabutyl titanate, adding glacial acetic acid and dilute nitric acid, sealing and stirring to form TiO2Sol-gel;
(4) mixing NiFe2O4-CoFe2O4Dropwise addition of the solution to TiO2And (2) adding the graphite oxide ground in the step (1) into the sol-gel, and stirring, filtering and drying to obtain the graphite oxide nanoparticle electrode material.
4. The preparation method according to claim 3, wherein in the step (1), the mass ratio of the graphite oxide to the hydrazine hydrate is 10 (8-9), and the pH is adjusted to 8.
5. The method according to claim 3, wherein in the step (2), the cobalt nitrate hexahydrate and the iron nitrate nonahydrate are each CoFe2O4Weighing the Co to Fe with the medium atomic ratio of 1 to 2; the mass-volume ratio of the cobalt nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL to 3 mL.
6. The method according to claim 3, wherein in the step (2), the nickel nitrate hexahydrate and the iron nitrate nonahydrate are NiFe2O4Weighing Ni and Fe in the ratio of 1: 2; the mass-volume ratio of the nickel nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL to 3 mL.
7. The preparation method according to claim 3, wherein in the step (3), the volume ratio of the absolute ethyl alcohol to the tetrabutyl titanate is 1 (1-2).
8. The preparation method according to claim 3, wherein in the step (3), the volume ratio of the absolute ethyl alcohol to the glacial acetic acid to the dilute nitric acid is 10:3:10, and the concentration of the dilute nitric acid is 1 mol/L.
9. The preparation method according to claim 3, wherein the sealed stirring is performed for 1 hour at 40 ℃ on a constant-temperature magnetic stirrer.
10. The preparation method according to claim 3, wherein in the step (4), the drying is carried out at 120-160 ℃ for 24 h.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1186846A (en) * | 1997-07-07 | 1999-03-30 | Asahi Chem Ind Co Ltd | Battery positive electrode |
CN102744068A (en) * | 2012-07-20 | 2012-10-24 | 常州大学 | Magnetic-separable titanium dioxide P25-ferrite-graphene nanometer catalyst and preparation method thereof |
US20130323608A1 (en) * | 2012-05-31 | 2013-12-05 | China Petrochemical Development Corporation, Taipei (Taiwan) | Electrolyte solution having ionic liquid and lithium-ion battery having the same |
CN104269520A (en) * | 2014-09-24 | 2015-01-07 | 南京工业大学 | Li2FeTiO4-G composite positive electrode material taking graphene as carrier and preparation method of Li2FeTiO4-G composite positive electrode material |
US20170054138A1 (en) * | 2015-08-21 | 2017-02-23 | Korea Advanced Institute Of Science And Technology | Ultra-high output power and extremely robust cycle life negative electrode material for lithium secondary battery and method for manufacturing the same, using layer structure of metal oxide nanoparticles and porous graphene |
CN107705998A (en) * | 2017-10-16 | 2018-02-16 | 浙江工业大学 | A kind of ferrite@graphenes hydrogel composite material and its application in electrochemical energy storage field |
WO2018066628A1 (en) * | 2016-10-05 | 2018-04-12 | 学校法人関西学院 | Metal compound – graphene oxide complex |
CN112993278A (en) * | 2021-02-05 | 2021-06-18 | 青岛科技大学 | Flower-shaped titanium dioxide/reduced graphene composite carrier supported platinum and alloy catalyst thereof, and preparation and application thereof |
-
2021
- 2021-12-10 CN CN202111505720.XA patent/CN114180680B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1186846A (en) * | 1997-07-07 | 1999-03-30 | Asahi Chem Ind Co Ltd | Battery positive electrode |
US20130323608A1 (en) * | 2012-05-31 | 2013-12-05 | China Petrochemical Development Corporation, Taipei (Taiwan) | Electrolyte solution having ionic liquid and lithium-ion battery having the same |
CN102744068A (en) * | 2012-07-20 | 2012-10-24 | 常州大学 | Magnetic-separable titanium dioxide P25-ferrite-graphene nanometer catalyst and preparation method thereof |
CN104269520A (en) * | 2014-09-24 | 2015-01-07 | 南京工业大学 | Li2FeTiO4-G composite positive electrode material taking graphene as carrier and preparation method of Li2FeTiO4-G composite positive electrode material |
US20170054138A1 (en) * | 2015-08-21 | 2017-02-23 | Korea Advanced Institute Of Science And Technology | Ultra-high output power and extremely robust cycle life negative electrode material for lithium secondary battery and method for manufacturing the same, using layer structure of metal oxide nanoparticles and porous graphene |
WO2018066628A1 (en) * | 2016-10-05 | 2018-04-12 | 学校法人関西学院 | Metal compound – graphene oxide complex |
CN109715291A (en) * | 2016-10-05 | 2019-05-03 | 学校法人关西学院 | Metallic compound-graphene oxide complex |
CN107705998A (en) * | 2017-10-16 | 2018-02-16 | 浙江工业大学 | A kind of ferrite@graphenes hydrogel composite material and its application in electrochemical energy storage field |
CN112993278A (en) * | 2021-02-05 | 2021-06-18 | 青岛科技大学 | Flower-shaped titanium dioxide/reduced graphene composite carrier supported platinum and alloy catalyst thereof, and preparation and application thereof |
Non-Patent Citations (1)
Title |
---|
翟倩楠等: "氧化石墨烯的制备、结构控制与应用", 《化工进展》 * |
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