CN107913667B - Magnetic graphene/ferroferric oxide/manganese dioxide nanocomposite and preparation and application thereof - Google Patents

Magnetic graphene/ferroferric oxide/manganese dioxide nanocomposite and preparation and application thereof Download PDF

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CN107913667B
CN107913667B CN201711008658.7A CN201711008658A CN107913667B CN 107913667 B CN107913667 B CN 107913667B CN 201711008658 A CN201711008658 A CN 201711008658A CN 107913667 B CN107913667 B CN 107913667B
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吴礼光
姚远
李春娟
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Zhejiang Gongshang University
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Abstract

The invention discloses a magnetic graphene/ferroferric oxide/manganese dioxide nanocomposite and a preparation method and application thereof, wherein the magnetic graphene/ferroferric oxide/manganese dioxide nanocomposite is prepared by the following steps: (1) dispersing graphene oxide and polyethylene glycol in purified water in a constant-temperature water bath, and ultrasonically forming a uniform suspension: (2) FeCl is added dropwise3And FeCl2Continuously reacting for 4-6 hours in an oxygen-free environment, then adding ammonia water to adjust the pH value to 10.5-11.5, raising the temperature of the water bath to 70-80 ℃, and continuously reacting for 2-3 hours to obtain a mixed solution; (3) adding MnSO into the obtained mixed solution4The solution was then KMnO added4And KOH, reacting for 2-4 hours, and then carrying out post-treatment to obtain the catalyst. The invention takes graphene sheet layers as carriers, and Fe is sequentially precipitated and grown on the graphene sheet layers in situ3O4And MnO2Nanoparticles to prevent agglomeration of graphene; meanwhile, the lamellar structure of graphene oxide is used as Fe3O4And MnO2Immobilization of nanoparticles to support against Fe3O4And MnO2And (4) agglomeration of the nano particles. The invention provides a nano composite materialThe method has the characteristics of environmental protection, rapidness, simplicity and convenience.

Description

Magnetic graphene/ferroferric oxide/manganese dioxide nanocomposite and preparation and application thereof
Technical Field
The invention belongs to the technical field of nano materials and environmental science, and particularly relates to magnetic rGO/Fe with adsorption and catalytic degradation functions3O4/MnO2Nanocomposite materials and applications thereof.
Background
The dye is widely applied to industries such as textile, leather, papermaking, printing, cosmetics and the like, and according to statistics, the annual output of the dye in China is about 75 ten thousand tons, which is the first in the world. About 10-15% of dye is released to the environment in the production and use processes, and the water body safety problem caused by dye pollution has attracted extensive attention. Generally, dye molecules have complex aromatic structures and are stable, and are difficult to naturally degrade in an aqueous environment. At present, the treatment methods of dye wastewater mainly comprise an adsorption method, a membrane separation method, catalytic oxidation degradation and the like. The adsorption method is an important technology for advanced wastewater treatment, and among a plurality of adsorbents, activated carbon is widely applied to dye wastewater treatment. But the active carbon has the defects of small adsorption quantity, high activation temperature, wide pore distribution, poor mechanical property, difficult regeneration, difficult surface modification and the like. The carbon nano material has high specific surface area and good chemical stability, and shows great potential and attractive application prospect in the adsorption of pollutants in wastewater.
The graphene is a novel two-dimensional nano material, has large specific surface area, and can reach 2630m in theoretical calculation2Has super strong adsorption capacity. Ramesha et al (Ramesha G K, Vijaya Kumara A, Muralidhara H B, Sampath S, Graphene and Graphene Oxide as Effective additives to heated agricultural and cationic Dyes, Journal of Colloid and Interface Science,2011,361, 270-plus 277) found that a very strong complexation reaction can be generated between Graphene and organic dye, thereby having a very strong adsorption capacity to organic dye. However, due to the nano-sheet structure of graphene, graphene is difficult to separate and recover in water and is easy to leak into the environment, so that health and environmental problems are caused. In addition, due to van der waals effect between graphene sheets, the graphene sheets are easy to agglomerate in a water body, so that the effective surface area is reduced, and the adsorption capacity is reduced. Therefore, the development of graphene or graphene composite materials which are hydrophilic and easy to recover is the research and development direction of novel graphene-based adsorption functional materials.
Wang et al (ZHao Guixia, Jiang, Lang He, Yu Dong, Li Jianxing, Dong Huangli, WangXiangke, Hu Wenping, Sulfonated Graphene for Persistent Aromatic polar functionalization, Advanced Materials,2011,23(34), 3959-. Research results show that the adsorption capacity of the functionalized graphene to naphthalene and naphthol reaches 2.4 mmol/g, and the graphene is a material with higher adsorption capacity at present.
The magnetic adsorption material has good adsorption capacity, can be separated from a water body through an external magnetic field, and has become a new generation material for environmental purification in recent years.
Catalytic oxidative degradation is also one of the effective methods for removing organic pollutants. Compared with the adsorption method, the catalytic oxidation method utilizes the catalyst to degrade the organic pollutants in the water body, thereby achieving the purpose of environmental management. MnO2Has a high oxidation potential, can oxidize a plurality of organic compounds, and is widely applied to water treatment as an oxidant. But MnO of2The apparent density of the composite is small, ultrafine particles are easily formed in water, and solid-liquid separation is difficult to realize after the composite is used.
Disclosure of Invention
The invention provides a magnetic rGO/Fe3O4/MnO2The nano composite material and the preparation method and the application thereof have good adsorption and catalytic degradation functions.
A preparation method of a magnetic graphene/ferroferric oxide/manganese dioxide nano composite material comprises the following steps:
(1) dispersing graphene oxide and polyethylene glycol in purified water in a constant-temperature water bath at 20-40 ℃, and ultrasonically forming a uniform suspension:
(2) continuously stirring the suspension in a constant-temperature water bath at 20-40 ℃, removing oxygen, and then dropwise adding FeCl3And FeCl2The mixed solution is continuously reacted for 4-6 hours in an oxygen-free environment, then ammonia water is added to adjust the pH value to 10.5-11.5, the stirring speed is increased, the water bath temperature is increased to 70-80 ℃, and the reaction is continuously carried out for 2-3 hours to obtain the rGO/Fe-containing solution3O4The mixed solution of (1);
(3) keep stirringThe stirring speed and the water bath temperature are unchanged, and MnSO is added into the obtained mixed solution4Solution, then quickly adding KMnO4Reacting the mixed solution with KOH for 2 to 4 hours to obtain the product containing rGO/Fe3O4/MnO2The mixed solution of (1);
(4) will contain rGO/Fe3O4/MnO2Repeatedly filtering and washing the mixed solution, and then carrying out heat treatment for 20-25 hours in a vacuum drying oven at the temperature of 140-160 ℃ to obtain the nano-silver/nano-silver.
The invention takes graphene sheet layers as carriers, and Fe is sequentially precipitated and grown on the graphene sheet layers in situ3O4And MnO2Nanoparticles, using in-situ grown Fe3O4And MnO2The nanoparticles prevent the graphene from agglomerating; meanwhile, the lamellar structure of graphene oxide is used as Fe3O4And MnO2Immobilization of nanoparticles to support against Fe3O4And MnO2And (4) agglomeration of the nano particles.
The invention uses GO as a carrier, and FeCl is selected firstly3And FeCl2Is used as a precursor, PEG is used as a reducing agent and a nanoparticle dispersion stabilizer, and the rGO/Fe is prepared by a precipitation method3O4Nanocomposite with MnSO4And KMnO4As a precursor, the rGO/Fe is prepared by a precipitation method3O4/MnO2A nanocomposite material. rGO/Fe prepared by the invention3O4/MnO2The nano composite material is used for adsorption and photocatalytic degradation removal of dye wastewater, shows good removal performance, and can be separated and recovered from a water body by using an external magnetic field.
The novelty of the present invention is represented by the prepared rGO/Fe3O4/MnO2Nanocomposite of GO, Fe3O4And MnO with MnO2The nano composite material not only has excellent dye adsorption capacity, but also has good photocatalytic degradation performance, and simultaneously has certain magnetism, and can be separated and recovered from a water body by using an external magnetic field. The invention provides rGO/Fe3O4/MnO2Nanocomposite processHas the characteristics of environmental protection, rapidness, convenience and the like.
Preferably, the ratio of the mass of GO added in the step (1) to the volume of purified water is 1/1.5-1/2.0 mg/mL, the oxygen content in GO is 4.5-6.5%, GO can be obtained commercially, or can be prepared by a Hummers method (D.C.Marcano, D.V.Kosynkin, J.M.Berlin, et al.improved synthesis of graphene oxide [ J ]. ACSNano,2010,4: 4806-); the mass ratio of the added PEG to GO is 5-10, and PEG is preferably PEG-400, PEG-600 and PEG-800.
The ratio of the mass of graphene oxide to the volume of purified water in step (1) is further preferably 1 mg: 1.7-1.8 mL.
Preferably, FeCl is used in step (2)2The mass ratio of the carbon to GO is 1/1-1.5/1; FeCl3With FeCl2The molar ratio was 2/1.
Preferably, MnSO is used in step (3)4With FeCl2And FeCl3The total mass ratio is 0.6/1-0.75/1; KMnO4With MnSO4The mass ratio is 1/1.1-1/1.2; KOH and MnSO4And KMnO4The total mass ratio is 0.9/1 to 1/1.
Preferably, the ultrasonic treatment time in the step (1) is 45-60 min, and more preferably 1 hour.
Preferably, in the step (2), the stirring speed in the constant-temperature water bath at the temperature of 20-40 ℃ is 1400-1600 rpm; the stirring speed in a constant temperature water bath at 70-80 ℃ is 2800-3200 rpm.
Preferably, the aqueous ammonia used in step (2) is a 25mg/mL aqueous ammonia solution.
Preferably, the temperature of the constant-temperature water bath in the step (1) is 30 ℃; in the step (2), the temperature is 30 ℃ before temperature rise and 75 ℃ after temperature rise.
Further preferably, the stirring speed in the 30 ℃ constant-temperature water bath in the step (2) is 1500 rpm; the stirring speed in a thermostatic water bath at 75 ℃ is 3000 rpm.
Further preferably, the step (2) is:
introducing N into the suspension obtained in the step (1) in a constant-temperature water bath at the temperature of 30 ℃ under the magnetic stirring of 1500rpm2Deoxidizing for 1 hour, then slowly adding FeCl dropwise3And FeCl2FeCl2The mass ratio of the carbon to GO is 1/1-1.5/1;FeCl added3With FeCl2The molar ratio is 2/1, stirring is continued and N is introduced2Deoxidizing for 5 hours, then quickly adding an ammonia water solution with the ammonia concentration of 25mg/mL to adjust the pH value to about 11, then adjusting the magnetic stirring to 3000rpm, raising the water bath temperature to 75 ℃, and reacting for 3 hours to obtain the product containing rGO/Fe3O4The mixed solution of (1).
Further preferably, the step (3) is:
adding MnSO into the mixed solution obtained in the step (2) in a constant-temperature water bath at 75 ℃ under magnetic stirring of 3000rpm4Solution, then quickly adding KMnO4Reacting the mixed solution with KOH for 3 hours to obtain a mixed solution containing rGO/Fe3O4/MnO2Mixed liquid of (2), MnSO4With FeCl2And FeCl3The total mass ratio is 0.6/1-0.75/1, and KMnO is added4With MnSO4The mass ratio is 1/1.1-1/1.2; KOH and MnSO are added4And KMnO4The total mass ratio is 0.9/1 to 1/1.
Further preferably, the step (4) is:
filtering the mixed solution obtained in the step (3) by using a filter flask, and washing the filtered sediment for multiple times by using purified water; finally, placing the product obtained after filtration and washing in a vacuum oven at 150 ℃ for heat treatment for 24 hours to obtain rGO/Fe3O4/MnO2A nanocomposite material.
Compared with the prior art, the invention has the following advantages:
the invention adopts a two-step precipitation method to prepare rGO/Fe3O4/MnO2Nanocomposite material, in the preparation of the composite, Fe3O4And MnO2The nano particles are precipitated and grown in situ between graphene sheets, and Fe is immobilized and dispersed by utilizing the two-dimensional planar structure of graphene oxide3O4And MnO2Nanoparticles while preventing agglomeration of graphene oxide lamellae. Prepared rGO/Fe3O4/MnO2Nanocomposite of GO, Fe3O4And MnO with MnO2Shows excellent dye adsorption energy by the nano-composite and mutual synergistic effectThe force and the photocatalytic degradation performance, and the separation and the recovery of an external magnetic field from a water body.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) photograph of nanocomposites prepared according to the present invention in example 1, comparative example 2, comparative example 3, and comparative example 4. (A: example 1; B: comparative example 1; C: comparative example 2; D: comparative example 3; E: comparative example 4)
FIG. 2 is a Raman spectrum (Raman) chart of the nanocomposites prepared in example 1, comparative example 2, and comparative example 4 of the present invention. Example 1 rGO/Fe3O4/MnO2(I); comparative example 2 rGO/MnO2(ii) a Comparative example 1 rGO/Fe3O4(ii) a COMPARATIVE EXAMPLE 4 rGO)
FIG. 3 is a hysteresis loop of nanocomposites prepared in example 1 of the invention and comparative example 1. Example 1 Fe3O4/MnO2/rGO (I); comparative example 1 rGO/Fe3O4)
Detailed Description
The following description is of preferred embodiments of the invention and is not intended to limit the invention thereto.
The following specific examples further illustrate how to prepare rGO/Fe using the present invention3O4/MnO2Nanocomposite materials, and their dye adsorption capacity and photocatalytic degradation properties.
1.rGO/Fe3O4/MnO2Evaluation of dye adsorption Property of nanocomposite:
in the experiment, Methylene Blue (MB) is selected as a target object to carry out rGO/Fe3O4/MnO2And (3) evaluating the adsorption performance of the nano composite material, namely adding 8mg of MB and 80mL of purified water into a 250mL conical flask to prepare an MB solution, and then adding 50mg of ultrasonically dispersed rGO/Fe3O4/MnO2Adding into the above mixed solution, and magnetically stirring in 30 deg.C constant temperature water bath. 2mL of the solution was aspirated every 5min by a disposable syringe, filtered through a 0.45 μm filter, the absorbance of the filtrate (λ 664nm) was measured by a spectrophotometer, and MB in the filtrate was calculated by Lambert beer's lawAnd the adsorption removal rate of MB was calculated from the following equation.
Adsorption removal rate (c)0-ct)/c0
In the formula, c0Initial concentration of MB; c. Ct:Concentration of MB after t minutes of adsorption.
2.rGO/Fe3O4/MnO2Evaluation of the catalytic degradation performance of the dye of the nanocomposite:
in the experiment, Methylene Blue (MB) is selected as a target object to carry out rGO/Fe3O4/MnO2And (3) evaluating the catalytic degradation of the nano composite material, namely adding 8mg of MB and 80mL of purified water into a 250mL conical flask to prepare an MB solution, adjusting the pH to 5.0 by using 0.1mg/L HCl solution, and adding 50mg of ultrasonically dispersed rGO/Fe3O4/MnO2Placing in 30 ℃ constant temperature water bath, magnetically stirring for 30min until the adsorption is balanced, measuring 2mL and 30% H2O2Adding into the above mixture, and reacting for 60 min. 2mL of the reaction solution was aspirated every 5min with a disposable syringe, filtered through a 0.45 μm filter, the absorbance (λ 664nm) of the filtrate was measured with a spectrophotometer, the concentration of MB in the filtrate was calculated by Lambert beer's law, and the catalytic degradation removal rate of MB was calculated from the following formula.
Removal rate of catalytic degradation ═ C0-Ct)/C0
In the formula, C0Initial concentration of MB; ct:MB concentration after t minutes of reaction.
Example 1
200mg of GO (containing 5.2 wt% of oxygen functional groups) and 1000mg of PEG-600 are respectively weighed and dissolved in 350ml of deionized water, and the mixture is subjected to ultrasonic treatment at 30 ℃ for 1 hour to form a uniform suspension. Magnetic stirring at 1500rpm and introducing N2Removing oxygen for 1 hour, and adding FeCl at the concentrations of 100mg/mL (0.789mmol/mL) and 256mg/mL (1.578mmol/mL) at 30 deg.C2And FeCl32mL of the mixed solution was slowly added dropwise to the suspension, and stirring was continued while introducing N2After 5 hours of oxygen removal, ammonia at an ammonia concentration of 25mg/mL was rapidly added to adjust the pH to 11, the magnetic stirring rate was then adjusted to 3000rpm, and the temperature of the thermostatic water bath was raised to 75 ℃ for 3 hours.Under the magnetic stirring action of 3000rpm, adding MnSO with the concentration of 120mg/mL into the mixed solution in a constant-temperature water bath at the temperature of 75 DEG C44mL of the solution is added with KMnO with the concentration of 60mg/mL and 120mg/mL respectively4And 7mL of a mixed solution of KOH, and reacted for 3 hours. Filtering the obtained mixture with a filter flask, and washing the filtered sediment with purified water for multiple times; finally, placing the product obtained after filtering and washing in a vacuum oven at 50 ℃ for drying for 24 hours to obtain rGO/Fe3O4/MnO2A nanocomposite material.
rGO/Fe prepared in this example3O4/MnO2A Transmission Electron Microscope (TEM) photograph of the nanocomposite is shown as A in FIG. 1; prepared rGO/Fe3O4/MnO2A Raman spectroscopy (Raman) graph of the nanocomposite is shown in fig. 2.
rGO/Fe prepared in this example3O4/MnO2The dye adsorption and catalytic degradation properties of the nanocomposite are shown in table 1.
Example 2
200mg of GO (containing 5.2 wt% of oxygen functional groups) and 1200mg of PEG-600 are respectively weighed and dissolved in 350ml of deionized water, and the mixture is subjected to ultrasonic treatment at 30 ℃ for 1 hour to form a uniform suspension. Magnetic stirring at 1500rpm and introducing N2Removing oxygen for 1 hour, and adding FeCl at the concentrations of 100mg/mL (0.789mmol/mL) and 256mg/mL (1.578mmol/mL) at 30 deg.C2And FeCl32.5mL of the mixed solution was slowly added dropwise to the above suspension, and stirring was continued while introducing N2After 5 hours of oxygen removal, ammonia at an ammonia concentration of 25mg/mL was rapidly added to adjust the pH to 11, the magnetic stirring rate was then adjusted to 3000rpm, and the temperature of the thermostatic water bath was raised to 75 ℃ for 3 hours. Under the magnetic stirring action of 3000rpm, adding MnSO with the concentration of 120mg/mL into the mixed solution in a constant-temperature water bath at the temperature of 75 DEG C44.5mL of the solution was added to KMnO solution at 60mg/mL and 120mg/mL, respectively48mL of a mixed solution of KOH and the resultant was reacted for 3 hours. Filtering the obtained mixture with a filter flask, and washing the filtered sediment with purified water for multiple times; finally, the product obtained after filtration and washing is placed in a vacuum oven at 50 ℃ for drying24 hours, get rGO/Fe3O4/MnO2A nanocomposite material.
rGO/Fe prepared in this example3O4/MnO2The dye adsorption and catalytic degradation properties of the nanocomposite are shown in table 1.
Example 3
200mg of GO (containing 5.2 wt% of oxygen functional groups) and 1400mg of PEG-600 are respectively weighed and dissolved in 350ml of deionized water, and the mixture is subjected to ultrasonic treatment at 30 ℃ for 1 hour to form a uniform suspension. Magnetic stirring at 1500rpm and introducing N2Removing oxygen for 1 hour, and adding FeCl at the concentrations of 100mg/mL (0.789mmol/mL) and 256mg/mL (1.578mmol/mL) at 30 deg.C2And FeCl33mL of the mixed solution of (2) was slowly added dropwise to the above suspension, and stirring was continued while introducing N2After 5 hours of oxygen removal, ammonia at an ammonia concentration of 25mg/mL was rapidly added to adjust the pH to 11, the magnetic stirring rate was then adjusted to 3000rpm, and the temperature of the thermostatic water bath was raised to 75 ℃ for 3 hours. Under the magnetic stirring action of 3000rpm, adding MnSO with the concentration of 120mg/mL into the mixed solution in a constant-temperature water bath at the temperature of 75 DEG C46mL of the solution is added with KMnO with the concentration of 60mg/mL and 120mg/mL respectively4And 11mL of a mixed solution of KOH, and reacted for 3 hours. Filtering the obtained mixture with a filter flask, and washing the filtered sediment with purified water for multiple times; finally, placing the product obtained after filtering and washing in a vacuum oven at 50 ℃ for drying for 24 hours to obtain rGO/Fe3O4/MnO2A nanocomposite material.
rGO/Fe prepared in this example3O4/MnO2The dye adsorption and catalytic degradation properties of the nanocomposite are shown in table 1.
Comparative example 1
200mg of GO (containing 5.2 wt% of oxygen functional groups) and 1000mg of PEG-600 are respectively weighed and dissolved in 350ml of deionized water, and the mixture is subjected to ultrasonic treatment at 30 ℃ for 1 hour to form a uniform suspension. Magnetic stirring at 1500rpm and introducing N2Removing oxygen for 1 hour, and adding FeCl at the concentrations of 100mg/mL (0.789mmol/mL) and 256mg/mL (1.578mmol/mL) at 30 deg.C2And FeCl32mL of the mixed solution was slowly added dropwise to the above suspension,stirring is continued and N is introduced2After 5 hours of oxygen removal, ammonia at an ammonia concentration of 25mg/mL was rapidly added to adjust the pH to 11, the magnetic stirring rate was then adjusted to 3000rpm, and the temperature of the thermostatic water bath was raised to 75 ℃ for 3 hours. Filtering the obtained mixture with a filter flask, and washing the filtered sediment with purified water for multiple times; finally, placing the product obtained after filtering and washing in a vacuum oven at 50 ℃ for drying for 24 hours to obtain rGO/Fe3O4A nanocomposite material.
rGO/Fe prepared in this example3O4A Transmission Electron Microscope (TEM) photograph of the nanocomposite material is shown as B in fig. 1; prepared rGO/Fe3O4A Raman spectroscopy (Raman) graph of the nanocomposite is shown in fig. 2.
rGO/Fe prepared in this example3O4The dye adsorption and catalytic degradation properties of the nanocomposite are shown in table 1.
Comparative example 2
200mg of GO (containing 5.2 wt% of oxygen functional groups) and 1200mg of PEG-600 are respectively weighed and dissolved in 350ml of deionized water, and the mixture is subjected to ultrasonic treatment at 30 ℃ for 1 hour to form a uniform suspension. Under the magnetic stirring action of 3000rpm, adding MnSO with the concentration of 120mg/mL into the suspension in a constant-temperature water bath at the temperature of 75 DEG C44.5mL of the solution was added to KMnO solution at 60mg/mL and 120mg/mL, respectively48mL of a mixed solution of KOH and the resultant was reacted for 3 hours. Filtering the obtained mixed solution by using a filter flask, and washing the filtered sediment for multiple times by using purified water; finally, placing the product obtained after filtering and washing in a vacuum oven at 50 ℃ for drying for 24 hours to obtain rGO/MnO2A nanocomposite material.
rGO/MnO prepared in this example2A Transmission Electron Microscope (TEM) photograph of the nanocomposite material is shown as C in fig. 1; prepared rGO/MnO2A Raman spectroscopy (Raman) graph of the nanocomposite is shown in fig. 2.
rGO/MnO prepared in this example2The dye adsorption and catalytic degradation properties of the nanocomposite are shown in table 1.
Comparative example 3
1400mg are weighedPEG-600 was dissolved in 350ml of deionized water and sonicated at 30 ℃ for 1 hour to form a homogeneous solution. Magnetic stirring at 1500rpm and introducing N2Removing oxygen for 1 hour, and adding FeCl at the concentrations of 100mg/mL (0.789mmol/mL) and 256mg/mL (1.578mmol/mL) at 30 deg.C2And FeCl33mL of the mixed solution of (1) was slowly added dropwise to the above solution, and stirring was continued while introducing N2After 5 hours of oxygen removal, ammonia at an ammonia concentration of 25mg/mL was rapidly added to adjust the pH to 11, the magnetic stirring rate was then adjusted to 3000rpm, and the temperature of the thermostatic water bath was raised to 75 ℃ for 3 hours. Under the magnetic stirring action of 3000rpm, adding MnSO with the concentration of 120mg/mL into the mixed solution in a constant-temperature water bath at the temperature of 75 DEG C46mL of the solution is added with KMnO with the concentration of 60mg/mL and 120mg/mL respectively4And 11mL of a mixed solution of KOH, and reacted for 3 hours. Filtering the obtained mixture with a filter flask, and washing the filtered sediment with purified water for multiple times; finally, placing the product obtained after filtration and washing in a vacuum oven at 50 ℃ for drying for 24 hours to obtain Fe3O4/MnO2A nanocomposite material.
Fe prepared in this example3O4/MnO2A Transmission Electron Microscope (TEM) photograph of the nanocomposite material is shown in D in FIG. 1.
Fe prepared in this example3O4/MnO2The dye adsorption and catalytic degradation properties of the nanocomposite are shown in table 1.
Comparative example 4
200mg of GO (containing 5.2 wt% of oxygen functional groups) and 1000mg of PEG-600 are respectively weighed and dissolved in 350ml of deionized water, and the mixture is subjected to ultrasonic treatment at 30 ℃ for 1 hour to form a uniform suspension. Filtering the obtained suspension by using a suction flask, and washing the filtered sediment for multiple times by using purified water; and finally, placing the product obtained after filtering and washing in a vacuum oven at 50 ℃ for drying for 24 hours to obtain the rGO nano material.
A Transmission Electron Microscope (TEM) photograph of the rGO nanomaterial prepared in this example is shown as E in fig. 1.
FIG. 1 is rGO/Fe3O4、rGO/MnO2、rGO/Fe3O4/MnO2TEM micrograph with rGO. From E in fig. 1, it can be seen that rGO exhibits a fully exfoliated, translucent sheet yarn-like structure. From D, C, B, A in FIG. 1, Fe can be seen3O4/MnO2、Fe3O4、MnO2Are all in the shape of spherical nano particles and Fe3O4、MnO2、Fe3O4/MnO2The nanoparticles are distributed on the rGO sheet layer more uniformly.
As can be seen from FIG. 2, rGO and rGO/Fe3O4、rGO/MnO2、rGO/Fe3O4/MnO2The Raman spectra of the light source are all 1350cm-1And 1580cm-1A defect appeared in the region of 1350cm-1Defect peak (D peak) of (1), which is reflected by lattice defect (sp) of carbon atoms in rGO sheet layer3Defect or amorphous carbon, 1580cm-1Defect peak (G peak) at (C) is corresponding to the sp atom of the rGO sheet2Hybrid in-plane stretching vibration. Raman spectrum from sample and I thereofD/IGThe value can be clearly obtained, adding Fe3O4、MnO2、Fe3O4/MnO2After rGO ID/IGThe increased value is due to the formation of smaller size nanoparticles on the rGO sheet, resulting in sp2Reduced average area of hybridized carbon atoms, resulting in ID/IGThe value increases.
FIG. 3 is a hysteresis loop of the nanocomposites prepared in example 1 and comparative example 1, showing rGO/Fe prepared by the method3O4/MnO2、rGO/Fe3O4All have stronger magnetism, and can be separated and recovered from the water body through an external magnetic field.
The dye adsorption and catalytic degradation properties of the rGO nanomaterial prepared in this example are shown in table 1.
Table 1 shows rGO/Fe prepared in examples of the invention3O4/MnO2The dye adsorption and catalytic degradation performance of the nano composite material and the nano composite materials prepared in comparative example 1, comparative example 2, comparative example 3 and comparative example 4.
TABLE 1
Figure BDA0001445011990000101
The rGO/Fe values produced in examples 1-3 are shown in Table 13O4/MnO2Nanocomposite, rGO/Fe prepared separately for comparative examples 1-43O4Nanocomposite, rGO/MnO2Nanocomposite material, Fe3O4/MnO2Nanocomposite, MB adsorption removal rate and catalytic degradation removal rate of GO. With rGO/Fe3O4Nanocomposite, rGO/MnO2Nanocomposite material, Fe3O4/MnO2Nanocomposite, GO phase comparison, rGO/Fe3O4/MnO2The nano composite material not only has excellent dye adsorption capacity, but also has good photocatalytic degradation performance, and simultaneously has certain magnetism, and can be separated and recovered from a water body by using an external magnetic field.

Claims (7)

1. A preparation method of a magnetic graphene/ferroferric oxide/manganese dioxide nanocomposite is characterized by comprising the following steps:
(1) dispersing graphene oxide and polyethylene glycol in purified water in a constant-temperature water bath at 20-40 ℃, and performing ultrasonic treatment to form a uniform suspension;
(2) continuously stirring the suspension in a constant-temperature water bath at 20-40 ℃, removing oxygen, and then dropwise adding FeCl3And FeCl2The mixed solution is continuously reacted for 4-6 hours in an oxygen-free environment, then ammonia water is added to adjust the pH value to 10.5-11.5, the stirring speed is increased, the water bath temperature is increased to 70-80 ℃, and the reaction is continuously carried out for 2-3 hours to obtain the rGO/Fe-containing solution3O4The mixed solution of (1); FeCl2The mass ratio of the graphene oxide to the graphene oxide is 1/1-1.5/1;
(3) keeping the stirring speed and the water bath temperature unchanged, and adding MnSO into the obtained mixed solution4Solution, then quickly adding KMnO4Reacting the mixed solution with KOH for 2 to 4 hours to obtain the product containing rGO/Fe3O4/MnO2The mixed solution of (1); MnSO4With FeCl2And FeCl3The total mass ratio is 0.6/1-0.75/1; KMnO4With MnSO4The mass ratio is 1/1.1-1/1.2; KOH and MnSO4And KMnO4The total mass ratio is 0.9/1-1/1;
(4) will contain rGO/Fe3O4/MnO2Repeatedly filtering and washing the mixed solution, and then carrying out heat treatment for 20-25 hours in a vacuum drying oven at the temperature of 140-160 ℃ to obtain the nano-silver/nano-silver.
2. The preparation method according to claim 1, wherein the ratio of the mass of graphene oxide to the volume of purified water in step (1) is 1 mg: 1.5-2.0 mL, the oxygen content in the graphene oxide is 4.5-6.5%, and the mass ratio of the polyethylene glycol to the graphene oxide is 5-10.
3. The method of claim 1, wherein FeCl is added in step (2)3With FeCl2The molar ratio was 2/1.
4. The preparation method according to claim 1, wherein the ultrasonic treatment time in the step (1) is 45-60 min.
5. The preparation method according to claim 1, wherein the stirring speed in the thermostatic water bath at 20-40 ℃ in the step (2) is 1400-1600 rpm; the stirring speed in a constant temperature water bath at 70-80 ℃ is 2800-3200 rpm.
6. The process according to claim 1, wherein the aqueous ammonia used in the step (2) is a 25mg/mL aqueous ammonia solution.
7. The method according to claim 1, wherein the temperature of the constant-temperature water bath in the step (1) is 30 ℃; in the step (2), the temperature is 30 ℃ before the temperature rise and 75 ℃ after the temperature rise.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101306864A (en) * 2008-06-25 2008-11-19 浙江工业大学 Degradation process for environment estrogenic pollutant in water body
CN102120619A (en) * 2011-01-11 2011-07-13 河北师范大学 Preparation method of brain-coral-shaped birnessite type manganese dioxide
CN103285874A (en) * 2013-06-13 2013-09-11 江苏中核华纬工程设计研究有限公司 Inorganic nano composite catalyst with peroxidase property and application of catalyst for performing catalytic decomposition on TMB thereof
CN103693639A (en) * 2013-12-13 2014-04-02 天津工业大学 Preparation method of iron/manganese oxide doped graphene composite material
CN104888706A (en) * 2015-06-08 2015-09-09 河海大学 Magnetically separable compound adsorbent as well as preparation method and application thereof
CN105289493A (en) * 2015-11-17 2016-02-03 辽宁大学 Ferromanganese modified straw active carbon adsorbent for As (III) adsorption, and applications thereof
CN106115796A (en) * 2016-06-29 2016-11-16 广西桂柳化工有限责任公司 Preparation method of graphene-manganese dioxide nano material containing magnetic iron
CN106140090A (en) * 2016-08-31 2016-11-23 南京尚易环保科技有限公司 A kind of MnO for removing indoor formaldehyde2aCF material and preparation method thereof
CN106531472A (en) * 2016-11-29 2017-03-22 桂林理工大学 Preparation method of polypyrrole/graphene/ manganese oxide composite materials

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9149833B2 (en) * 2013-06-19 2015-10-06 Indian Institute Of Technology Madras Metal nanoparticle decorated carbon nanotubes and methods of preparation and use

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101306864A (en) * 2008-06-25 2008-11-19 浙江工业大学 Degradation process for environment estrogenic pollutant in water body
CN102120619A (en) * 2011-01-11 2011-07-13 河北师范大学 Preparation method of brain-coral-shaped birnessite type manganese dioxide
CN103285874A (en) * 2013-06-13 2013-09-11 江苏中核华纬工程设计研究有限公司 Inorganic nano composite catalyst with peroxidase property and application of catalyst for performing catalytic decomposition on TMB thereof
CN103693639A (en) * 2013-12-13 2014-04-02 天津工业大学 Preparation method of iron/manganese oxide doped graphene composite material
CN104888706A (en) * 2015-06-08 2015-09-09 河海大学 Magnetically separable compound adsorbent as well as preparation method and application thereof
CN105289493A (en) * 2015-11-17 2016-02-03 辽宁大学 Ferromanganese modified straw active carbon adsorbent for As (III) adsorption, and applications thereof
CN106115796A (en) * 2016-06-29 2016-11-16 广西桂柳化工有限责任公司 Preparation method of graphene-manganese dioxide nano material containing magnetic iron
CN106140090A (en) * 2016-08-31 2016-11-23 南京尚易环保科技有限公司 A kind of MnO for removing indoor formaldehyde2aCF material and preparation method thereof
CN106531472A (en) * 2016-11-29 2017-03-22 桂林理工大学 Preparation method of polypyrrole/graphene/ manganese oxide composite materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Adsorption of As (III) and As (V) from water using magnetite Fe3O4-reduced graphite oxide-MnO2 nanocomposites";Xubiao Luo et al.;《Chemical Engineering Journal》;20120430;第187卷;第46-47页 *

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