CN114180680B - Graphite oxide nanoparticle electrode material and preparation method thereof - Google Patents

Graphite oxide nanoparticle electrode material and preparation method thereof Download PDF

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CN114180680B
CN114180680B CN202111505720.XA CN202111505720A CN114180680B CN 114180680 B CN114180680 B CN 114180680B CN 202111505720 A CN202111505720 A CN 202111505720A CN 114180680 B CN114180680 B CN 114180680B
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graphite oxide
electrode material
oxide nanoparticle
cofe
nife
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CN114180680A (en
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肖寒
黄操
罗迎春
谢雅典
王环江
周国永
代天军
黄伟
周章渝
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Guizhou Minzu University
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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
    • 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
    • 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, and belongs to the technical field of sewage treatment. The graphite oxide nanoparticle electrode material of the invention is based on NiFe 2 O 4 ‑CoFe 2 O 4 /TiO 2 A loaded graphite oxide nanoparticle electrode material. The preparation method comprises the following steps: preparation of graphite oxide, niFe 2 O 4 ‑CoFe 2 O 4 Preparation of solutions, tiO 2 Preparing sol gel; finally NiFe is added 2 O 4 ‑CoFe 2 O 4 Drop-adding solution to TiO 2 And adding the ground graphite oxide into the sol gel to obtain the graphite oxide nanoparticle electrode material. The graphite oxide nanoparticle electrode material has good photoelectric catalytic effect, can effectively degrade organic matters, has good heavy metal adsorption effect, and can be well applied to the wastewater treatment fields of printing and dyeing industry, textile industry and the like.

Description

Graphite oxide nanoparticle electrode material and preparation method thereof
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 global industry and agriculture, the wastewater discharged from 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 good treatment, and various pollutants contained in the wastewater can seriously influence the ecological environment and cause serious harm to water bodies and even human health.
At present, in a sewage treatment method by utilizing a photocatalytic semiconductor material, pure TiO 2 Photocatalytic oxidation technology still exists: the solar energy utilization rate is low, the photo-generated electron-hole pair recombination probability is high, and the separation and recovery are difficult. These problems have limited to a certain extent their use in practical water treatment. The noble metal is used for TiO in the market 2 Modified to enhance TiO 2 But precious metal resources are scarce and costly. Therefore, the research on the graphite oxide nano particle electrode material which has reasonable cost, good photoelectric catalytic 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, which are used for solving 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 good photoelectric catalytic effect, can effectively degrade organic matters, has good heavy metal adsorption effect, and can be well applied to the fields of wastewater treatment containing organic matters, organic dyes and heavy metals in the dyeing industry, textile industry and the like.
In order to achieve the above object, the present invention provides the following solutions:
it is an object of the present invention to provide a graphite oxide nanoparticle electrode material based on NiFe 2 O 4 -CoFe 2 O 4 /TiO 2 A loaded graphite oxide nanoparticle electrode material.
Further, niFe in the electrode material 2 O 4 -CoFe 2 O 4 、TiO 2 The mass ratio of the graphite oxide to the catalyst is (1-2): 1.
The second object of the invention is to provide a preparation method of the graphite oxide nanoparticle electrode material, which comprises the following steps:
(1) Mixing graphite oxide and hydrazine hydrate, regulating the pH value of the solution to be alkaline, and carrying out freezing, drying and grinding for later use;
（2）NiFe 2 O 4 -CoFe 2 O 4 preparation of the solution: dissolving cobalt nitrate hexahydrate and ferric nitrate nonahydrate in absolute ethyl alcohol, adding water, sealing and stirring to obtain dark red transparent solution A; dissolving nickel nitrate hexahydrate and ferric nitrate nonahydrate in absolute ethyl alcohol, adding water, sealing and stirring to obtain a light red transparent solution B; dropwise adding the solution A into the solution B, and stirring in a sealing manner to obtain NiFe 2 O 4 -CoFe 2 O 4 A solution;
（3）TiO 2 preparation of sol-gel: mixing absolute ethyl alcohol and tetrabutyl titanate, adding glacial acetic acid and dilute nitric acid, and stirring in a sealing manner to form TiO 2 Sol-gel;
(4) NiFe is mixed with 2 O 4 -CoFe 2 O 4 Drop-adding solution to TiO 2 Adding the ground graphite oxide into the sol gel, stirring for 1h, filtering and drying to obtain the graphite oxide nano particle electrode material.
Further, the specific preparation steps of the graphite oxide in the invention are as follows:
a. low temperature reaction stage: natural crystalline flake graphite (500 mesh) was added to concentrated sulfuric acid (98%), graphite: concentrated sulfuric acid = 1g:28ml, and reacted in an ice water bath for 5h (0 ℃);
b. medium temperature reaction stage: KMnO was added in two portions 4 KMnO graphite 4 (m/m) =1:3.5, every 1h interval, 70% of the total mass was added for the first time, and stirred overnight; the remaining 30% of KMnO was added for the second time 4 Heating to 40deg.C, continuing to react for 5 hr, adding ultrapure water, KMnO 4 Ultrapure water=14g:336 ml.
c. High temperature reaction stage: heating to 90 ℃, enabling the reaction solution to become golden yellow, reacting for 15-30 minutes, stopping heating when the reaction solution tends to deepen, and adding H 2 O 2 And (3) extracting the mixed water bath hot water until no bubbles are generated, changing the mixed water bath hot water into the hot water, stopping the reaction after the reaction is continuously stirred for 30 minutes, continuously adding pure water, and removing the supernatant after standing. Washing with dilute hydrochloric acid for 3 times, stirring and standing, removing supernatant, repeating the operation for 3 times, removing supernatant to obtain precipitate, washing with pure water, and centrifuging for 2-3 times until the pH of the supernatant is 3.
d. Mixing according to the mass ratio of graphite oxide to hydrazine hydrate of (8-9), regulating the pH value of the solution to 8, stirring for 80min at 100 ℃, freezing for 12h, drying for 24h, grinding and preserving in dark place.
Further, in step (2), the cobalt nitrate hexahydrate and the iron nitrate nonahydrate are mixed according to CoFe 2 O 4 The proportion of the medium atomic ratio Co to Fe=1:2 is weighed; the mass volume ratio of the cobalt nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL to 3mL.
Further, in step (2), the nickel nitrate hexahydrate and the iron nitrate nonahydrate are used as NiFe 2 O 4 The proportion of the medium atomic ratio Ni to Fe=1:2 is weighed; the mass volume ratio of the nickel nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL to 3mL.
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 1mol/L.
Further, the sealed stirring is carried out on a constant temperature magnetic stirrer at 40 ℃ for 1h.
Further, in the step (4), the drying is performed at 120-160 ℃ for 24 hours.
The invention discloses the following technical effects:
the graphite oxide of the inventionThe preparation method of the nanoparticle electrode material is simple, the raw materials are cheap and easy to obtain, and the sources are wide; niFe with Ni and Co metal as compound 2 O 4 、CoFe 2 O 4 Has higher catalytic activity and material stability in non-platinum-based transition metal compounds, and NiFe 2 O 4 -CoFe 2 O 4 Fe of (3) 2+ Can be combined with H 2 O 2 Reacts to generate active substance OH with strong oxidizing property to degrade organic matters and Fe generated simultaneously 3+ And (3) performing coagulating sedimentation reaction to remove part of organic matters. Easy loading of TiO in graphite oxide 2 Not only can widen the response range of visible light, but also can effectively separate photo-generated electrons and holes and improve TiO 2 Is used for the adsorption performance of the catalyst. Thus, niFe 2 O 4 -CoFe 2 O 4 /TiO 2 The nano particle electrode material loaded on the graphite oxide has a higher sewage treatment application prospect.
The graphite oxide nanoparticle electrode material has a good photoelectric catalytic effect, and can effectively degrade organic matters, such as: rhodamine B, malachite green and the like can be well applied to the fields of waste water treatment containing organic matters, organic dyes and heavy metals in the dyeing industry, 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 that are 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 other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of pure unsupported graphite oxide;
FIG. 2 is an SEM image of a graphite oxide nanoparticle electrode material of example 1;
FIG. 3 is a graph showing the effect of different nanoparticle electrodes on rhodamine B solution degradation rate;
figure 4 is a graph of fitting kinetics of different nanoparticle electrodes.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions 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. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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 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 invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
In the following examples, the specific preparation steps of graphite oxide are as follows:
a. low temperature reaction stage: natural crystalline flake graphite (500 mesh) was added to concentrated sulfuric acid (98%), graphite: concentrated sulfuric acid = 1g:28ml, and reacted in an ice water bath for 5h (0 ℃);
b. medium temperature reaction stage: KMnO was added in two portions 4 KMnO graphite 4 (m/m) =1:3.5, every 1h interval, 70% of the total mass was added for the first time, and stirred overnight; the remaining 30% of KMnO was added for the second time 4 Heating to 40deg.C, continuing to react for 5 hr, adding ultrapure water, KMnO 4 Ultrapure water=14g:336 ml.
c. High temperature reaction stage: heating to 90deg.C, reacting for 30 min, stopping heating, and adding H 2 O 2 And (3) pumping out the mixed water bath hot water until no bubbles appear, changing the mixed water bath hot water into normal-temperature (25 ℃) water, continuously stirring the reaction for 30 minutes, stopping the reaction, continuously adding pure water, and removing the supernatant after standing. 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 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, regulating the pH value of the solution to 8, and carrying out freezing, drying and grinding for later use;
（2）NiFe 2 O 4 -CoFe 2 O 4 preparation of the solution: according to CoFe 2 O 4 Cobalt nitrate hexahydrate and ferric nitrate nonahydrate are weighed according to the proportion of Co to Fe=1:2, dissolved in absolute ethyl alcohol, water is added, 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 the mixture is stirred for 1h at the temperature of 40 ℃ on a constant-temperature magnetic stirrer to obtain solution A; according to NiFe 2 O 4 The method comprises the steps of weighing nickel nitrate hexahydrate and ferric nitrate nonahydrate according to a proportion of Fe=1:2, dissolving the nickel nitrate hexahydrate and the ferric nitrate nonahydrate in absolute ethyl alcohol, adding water, stirring the nickel nitrate hexahydrate, the absolute ethyl alcohol and the water for 1h on a constant-temperature magnetic stirrer at 40 ℃ to obtain a solution B, wherein the mass volume ratio of the nickel nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g:20mL:3 mL; dropwise adding the solution A into the solution B, and stirring for 1h at 40 ℃ on a constant temperature magnetic stirrer to obtain NiFe 2 O 4 -CoFe 2 O 4 A solution;
（3）TiO 2 preparation 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 (1 mol/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 TiO 2 Sol-gel;
(4) NiFe is mixed with 2 O 4 -CoFe 2 O 4 Drop-adding solution to TiO 2 Adding ground graphite oxide and NiFe into sol-gel 2 O 4 -CoFe 2 O 4 、TiO 2 And graphite oxide with the mass ratio of 1:2:1, stirring, filtering, and drying at 150 ℃ for 24 hours to obtain the graphite oxide nano particle electrode material.
Fig. 1 is an SEM image of unsupported graphite oxide. FIG. 2 is an SEM image of a graphite oxide nanoparticle electrode material of the present example, and it can be seen from FIG. 2 that NiFe is prepared from the material, compared with a conventional graphite oxide nanoparticle electrode material prepared by a coprecipitation method 2 O 4 -CoFe 2 O 4 /TiO 2 The particles are dispersed, serious agglomeration is not easy to occur, and the particles are loaded on the graphite oxide, so that larger pores are generated after sintering, and the specific surface area of the graphite oxide nanoparticle electrode material is increased.
Experiment setting initial rhodamine B concentration at c0=10 mg/L, ph=7, 50mL rhodamine B solution was filled into a 100mL beaker, and the xenon lamp illumination intensity was 10 μw/m 2 Experiments were performed under conditions to examine the effect of example 1 and other particle electrodes on the rate of photoelectrocatalytic degradation of rhodamine B, and the results are shown in fig. 2.
As can be seen from FIG. 3, pure TiO after adsorption by dark reaction 2 Almost no adsorption capacity to rhodamine B, but NiFe is doped 2 O 4 -CoFe 2 O 4 TiO of (C) 2 Has certain adsorption to rhodamine B. Doped with NiFe 2 O 4 -CoFe 2 O 4 TiO of (C) 2 The capability of degrading rhodamine B under photocatalysis is obviously stronger than that of pure NiFe 2 O 4 Or CoFe 2 O 4 The degradation rate of rhodamine B reaches 90% almost after 60 min. The reason for this is that with NiFe 2 O 4 -CoFe 2 O 4 With TiO 2 The capability of the light source for exciting the photo-generated hole and electron pair generated by the composite material is gradually enhanced, and more photo-generated electricity and photo-generated hole with high activity are formed after the composite graphite oxide is added, more effective hydroxyl radical OH and superoxide anion O are generated 2 - Thereby enhancing the photocatalytic ability of the composite material.
As can be seen from FIG. 4, niFe 2 O 4 -CoFe 2 O 4 /TiO 2 The linear fit equation for graphite oxide is y=0.0479x+0.0026, r 2 The k value indicates the reaction rate constant, the larger the value, the faster the reaction. As is evident from the figure, niFe 2 O 4 -CoFe 2 O 4 /TiO 2 The reaction rate of graphite oxide is significantly greater than that of other types of materials.
Example 2
The difference from example 1 is that in step (1), graphite oxide and hydrazine hydrate are mixed in a mass ratio of 10:9.
Example 3
The difference from example 1 is that in step (3), absolute ethanol and tetrabutyl titanate are mixed in a volume ratio of 1:2.
Example 4
As in example 1, the difference is that in step (4), niFe 2 O 4 -CoFe 2 O 4 、TiO 2 And graphite oxide at a mass ratio of 2:1:1.
Comparative example 1
As in example 1, niFe was used 2 O 4 -CoFe 2 O 4 Replacement of solution with CoFe 2 O 4 A solution. In step (2), coFe is prepared 2 O 4 Solution: according to CoFe 2 O 4 Cobalt nitrate hexahydrate and ferric nitrate nonahydrate are weighed according to the proportion of Co to Fe=1 to 2, dissolved in absolute ethyl alcohol, and water is added, wherein the mass volume ratio of the cobalt nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL3mL, stirring at 40deg.C for 1h on a constant temperature magnetic stirrer to obtain CoFe 2 O 4 A solution. In step (4), coFe is added 2 O 4 Drop-adding solution to TiO 2 Adding the ground graphite oxide and CoFe into sol gel 2 O 4 、TiO 2 And graphite oxide with the mass ratio of 1:2:1, stirring, filtering, and drying at 150 ℃ for 24 hours to obtain the graphite oxide nano particle electrode material.
Comparative example 2
The difference with example 1 is that the graphite oxide is replaced by untreated natural crystalline flake graphite.
Detection method
The electrode materials of each example and comparative example were used for rhodamine B degradation by the following method: 100mL of rhodamine B solution is added into a condensing cup, and NiFe is added 2 O 4 -CoFe 2 O 4 /TiO 2 And (3) graphite oxide nanoparticle electrodes, wherein saturated sodium sulfate solution is used as electrolyte, adsorption balance is achieved after dark reaction is carried out for 1h, a 800W xenon lamp is used for simulating sunlight, a reactor is irradiated, a constant-current voltage-stabilizing power supply is used for regulating voltage, sampling is carried out every 10min, centrifugation is carried out for 5min under the condition that the rotating speed is 8000r/min, supernatant fluid is taken, the absorbance of the supernatant fluid is measured at the position of lambda=554 nm by a UV-visible spectrophotometer, the corresponding concentration is calculated according to a standard curve, and the degradation rate is calculated.
TABLE 1
Figure SMS_1
As shown in Table 1, the degradation rate of the graphite oxide nanoparticle electrode material of the invention on rhodamine B treatment for 60min can reach 90%. Comparative example 1 doping with CoFe alone 2 O 4 The electromagnetic wave absorption performance is poor, the capability of the light source for exciting photo-generated holes and electron pairs generated by the composite material is relatively weak, the photo-generated electricity and photo-generated holes with high activity are not easy to form, and hydroxyl free radical OH and superoxide anion O are not easy to generate 2 - Thereby affecting its photocatalytic ability. Comparative example 2 untreated natural crystalline flake graphite, flakesThe layers are tightly connected, the pores are smaller, and NiFe is not easy to insert 2 O 4 -CoFe 2 O 4 /TiO 2 Nanoparticle particles result in an insufficient specific surface area of the material.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.

Claims (9)

1. A graphite oxide nanoparticle electrode material is characterized in that the electrode material is based on NiFe 2 O 4 -CoFe 2 O 4 /TiO 2 A loaded graphite oxide nanoparticle electrode material;
the preparation method of the graphite oxide nanoparticle electrode material comprises the following steps:
(1) Mixing graphite oxide and hydrazine hydrate, regulating the pH value of the solution to be alkaline, and carrying out freezing, drying and grinding for later use;
（2）NiFe 2 O 4 -CoFe 2 O 4 preparation 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; dropwise adding the solution A into the solution B, and stirring in a sealing manner to obtain NiFe 2 O 4 -CoFe 2 O 4 A solution;
（3）TiO 2 preparation of sol-gel: mixing absolute ethyl alcohol and tetrabutyl titanate, adding glacial acetic acid and dilute nitric acid, and stirring in a sealing manner to form TiO 2 Sol-gel;
(4) NiFe is mixed with 2 O 4 -CoFe 2 O 4 Drop-adding solution to TiO 2 Adding the graphite oxide ground in the step (1) into sol gel, stirring, filtering and drying to obtain the graphite oxide nano particle electrode material。
2. A graphite oxide nanoparticle electrode material according to claim 1, wherein NiFe is present in the electrode material 2 O 4 -CoFe 2 O 4 、TiO 2 The mass ratio of the graphite oxide to the catalyst is (1-2): 1.
3. The graphite oxide nanoparticle electrode material according to claim 1, wherein in the step (1), the mass ratio of graphite oxide to hydrazine hydrate is 10 (8-9), and the pH is adjusted to 8.
4. The graphite oxide nanoparticle electrode material according to claim 1, wherein in step (2), the cobalt nitrate hexahydrate and the iron nitrate nonahydrate are as CoFe 2 O 4 The proportion of the medium atomic ratio Co to Fe=1:2 is weighed; the mass volume ratio of the cobalt nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL to 3mL.
5. The graphite oxide nanoparticle electrode material according to claim 1, wherein in step (2), the nickel nitrate hexahydrate and the iron nitrate nonahydrate are as NiFe 2 O 4 The proportion of the medium atomic ratio Ni to Fe=1:2 is weighed; the mass volume ratio of the nickel nitrate hexahydrate to the absolute ethyl alcohol to the water is 0.3g to 20mL to 3mL.
6. The graphite oxide nanoparticle electrode material according to claim 1, wherein in the step (3), the volume ratio of the absolute ethyl alcohol to the tetrabutyl titanate is 1 (1-2).
7. The graphite oxide nanoparticle electrode material according to claim 1, wherein in the step (3), the volume ratio of the absolute ethanol, the glacial acetic acid and the dilute nitric acid is 10:3:10, and the concentration of the dilute nitric acid is 1mol/L.
8. The graphite oxide nanoparticle electrode material of claim 1, wherein the sealed agitation is carried out at 40 ℃ for 1 hour on a constant temperature magnetic stirrer.
9. The graphite oxide nanoparticle electrode material according to claim 1, wherein in the step (4), the drying is performed at 120-160 ℃ for 24 hours.
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Citations (4)

* Cited by examiner, † Cited by third party
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
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
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

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI486309B (en) * 2012-05-31 2015-06-01 China Petrochemical Dev Corp Taipei Taiwan A lithium battery having an electrolyte solution containing an ionic liquid
KR101745449B1 (en) * 2015-08-21 2017-06-12 한국과학기술원 Hierarchical architecture with nanosized metal oxide and porous graphene for lithium ion battery anode with ultra-fast charge/discharge rate and extremely robust cycle life using thereof
JPWO2018066628A1 (en) * 2016-10-05 2019-08-29 学校法人関西学院 Metal compound-graphene oxide complex
CN107705998B (en) * 2017-10-16 2019-06-14 浙江工业大学 A kind of ferrite@graphene hydrogel composite material and its application in electrochemical energy storage field

Patent Citations (4)

* Cited by examiner, † Cited by third party
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
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
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)

* Cited by examiner, † Cited by third party
Title
氧化石墨烯的制备、结构控制与应用;翟倩楠等;《化工进展》;第39卷(第10期);第4061-4072页 *

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