CN102275903A - Preparation method of graphene and manganese dioxide nanocomposite - Google Patents
Preparation method of graphene and manganese dioxide nanocomposite Download PDFInfo
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Abstract
The invention relates to a preparation method of a graphene and manganese dioxide nano composite material, which comprises the following steps: (1) Uniformly stirring and mixing graphite, potassium nitrate and concentrated sulfur, adding potassium permanganate, reacting at 30-40 ℃ for 20-40 min, adding deionized water at room temperature, reacting for 15-30 min, and adding hydrogen peroxide to prepare graphite oxide; (2) Dispersing the graphite oxide in water, adding hydrazine hydrate, and reacting at 95 ℃ for 1-24 h to obtain graphene; (3) And ultrasonically dispersing the graphene into a saturated potassium permanganate solution, adding acid, and reacting at 60-80 ℃ for 1-5 h to obtain the graphene and manganese dioxide nanocomposite. The method has the advantages of simple reaction, easy control, convenient operation and simple process; the obtained composite material has wide application prospect, and can be used for catalysts, biosensing materials, electrode materials of lithium ion batteries, electrode materials of super capacitors and the like.
Description
Technical Field
The invention belongs to the field of preparation of manganese dioxide nano composite materials, and particularly relates to a preparation method of a graphene and manganese dioxide nano composite material.
Background
Manganese dioxide material, due to its structural diversity and its unique physicochemical properties, is also low in price, environmentally friendly, as an important electrode material, widely used in dry cells, alkaline manganese cells, zinc manganese cells, magnesium manganese cells, lithium manganese cells and other chemical power sources (CN 17584681594212 CN 95103067.1 CN 200510014876.2 CN 200810027780.3), as a multifunctional fine inorganic functional material, can be applied as molecular sieves, advanced catalyst materials and the like. As an amphoteric transition metal oxide, the amphoteric transition metal oxide has wide application in industrial production and environmental management, and has strong application prospect in the aspects of adsorbing and degrading organic pollutants and treating heavy metal wastewater containing mercury, cadmium, lead, chromium, metalloid arsenic and the like (CN 1935355A). In particular, the nano-scale manganese dioxide has a plurality of unique properties, such as a special microstructure, a larger specific surface area, a difference between a surface bond state and an electronic state and the inside of particles, and incomplete coordination of surface atoms, so that the surface active sites are increased, the surface smoothness is deteriorated along with the reduction of the particle size, uneven atomic steps are formed, and the contact surface of chemical reaction is increased. In particular, it has good electrochemical properties, excellent ionic/electronic conductivity and relatively high potential, making it very important for applications in the electrochemical field (CN 200410020888.1, CN 200510014876.2, CN 200910049408.7. The method for preparing the nano manganese dioxide is various, and mainly comprises a hydrothermal synthesis method, a low-temperature solid-phase synthesis method, an organic-water two-phase reaction method, a coprecipitation method, a reflux cooling method, a gel-sol method, a micro-emulsion method, a thermal decomposition method and the like, and particularly, a nano structure of a manganese dioxide sheet with high specific surface area is an important target pursued by synthesis work (CN 02157737.4, CN200810200287.7, CN 200910139589.2. However, most of the products obtained by the method are powder or particles with different shapes, the particle size distribution is wide, and the agglomeration phenomenon is serious. The serious agglomeration phenomenon exists in the process of storage and use of the nano manganese dioxide, so that the special performance and the advantages existing in a monodisperse state cannot be exerted. When the composite material is used as an electrode material, the defects of poor electronic conductivity, low utilization rate and the like of the single use of manganese dioxide exist, so that the nanometer manganese dioxide and a carbon-based material with a large specific surface area are often compounded together, the activity and the stability of the composite material can be further improved, and the synergistic effect of the nanometer manganese dioxide and the carbon-based material is exerted (CN 200410041356.6 CN 200610068772.4 CN 200710156155.4 CN 200911880.0 CN200910071963. X.
The graphene has a two-dimensional periodic honeycomb lattice structure consisting of carbon six-membered rings, has excellent electrical conductivity, thermal conductivity, mechanical properties and the like, and is an ideal carrier (CN 101800302A; CN101877405A; US 20100081057); chen Weixiang and the like, the graphene/Ru nanocomposite prepared by a hydrothermal method has higher specific capacitance as a supercapacitor electrode material, and when the content of Ru is 48.9%, the specific capacitance of the composite reaches 583F/g (CN 101714463A). The graphene also has good electrochemical stability, a large specific surface area and a wide electrochemical window, the specific layered structure of the graphene is favorable for rapid diffusion of electrolyte in the graphene, and instantaneous high-power charge and discharge of electronic elements are realized, and the graphene becomes a very potential lithium ion battery electrode material and a super capacitor electrode material (US 20100081057A1; CN101849302A; CN 1017494874A). He Yudan and the like, the graphene nanosheet-cobalt hydroxide composite negative electrode material of the lithium ion battery is prepared by a hydrothermal method, and when charging and discharging are carried out at a current of 200mA/g, the reversible specific capacity of the composite material can be stabilized to be more than 900mAh/g (CN 101867046A). Recently, yan et al prepare graphene/amorphous manganese dioxide composite materials by using a microwave radiation method, the graphene/amorphous manganese dioxide composite materials are excellent as electrode materials of high-speed scanning super capacitors, and the specific capacitance at 2mV/s is as high as 310F/gThe specific capacitance at 500mV/s is still as high as 228F/g (Carbon 2010; 48. Wu and the like are used for preparing the graphene/manganese dioxide nanowire composite material and are assembled into an electrochemical capacitor with excellent performance as a positive electrode material, and the volume ratio is 7.0Whkg -1 The power density of the generator is as high as 5000Wkg -1 After 1000 cycles, the specific capacitance decays to 21% (ACSNANO 2010; 4. Therefore, the nano manganese dioxide and the graphene are compounded to combine the excellent performances of the nano manganese dioxide and the graphene, and a remarkable synergistic effect is generated. The carbon nano tube is adopted as a carrier to successfully load the petal-shaped manganese dioxide nano crystal, and the material has a CV curve with obvious rectangular characteristics when being used as a super capacitor electrode, and has higher specific capacitance value and good electrochemical performance stability (CN 201010256458.5). At present, no literature report of loading the petal-shaped or rod-shaped manganese dioxide nanocrystals on graphene is found.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a graphene and manganese dioxide nano composite material, which has the advantages of simple reaction, easy control, convenient operation, simple process and convenient industrialization; the obtained composite material has wide application prospect, and can be used for catalysts, biosensing materials, electrode materials of lithium ion batteries, electrode materials of super capacitors and the like.
The invention discloses a preparation method of a graphene and manganese dioxide nanocomposite, which comprises the following steps:
(1) Uniformly stirring and mixing graphite, potassium nitrate and concentrated sulfuric acid in an ice water bath, adding potassium permanganate with the mass ratio of 1-5: 1 to the graphite, reacting for 20-40 min at 30-40 ℃, adding deionized water with the volume-mass ratio of 100-200 ml: 1g to the graphite at room temperature, reacting for 15-30 min, adding hydrogen peroxide with the volume-mass ratio of 10-30 ml: 1g to the graphite, and performing suction filtration and washing on the obtained product to neutrality to obtain graphite oxide; wherein the volume-to-volume ratio of the concentrated sulfuric acid to the graphite is 20-40 ml: 1g, and the mass-to-volume ratio of the potassium nitrate to the concentrated sulfuric acid is 20-50 g: 1L;
(2) Dispersing the graphite oxide in water to obtain graphite oxide dispersion liquid, adding hydrazine hydrate, wherein the volume mass ratio of the hydrazine hydrate to the graphite oxide is 1-3 ml: 1g, reacting at 95 ℃ for 1-24 h, and washing a product to be neutral to obtain graphene;
(3) Ultrasonically dispersing the graphene in a saturated potassium permanganate solution according to the mass ratio of 10-30: 1 to obtain a graphene dispersion solution, adding acid with the molar ratio of 2-5: 1 to potassium permanganate, carrying out ultrasonic auxiliary reaction at the temperature of 60-80 ℃ for 1-5 h, carrying out suction filtration and washing on the obtained product until the product is neutral, and carrying out vacuum drying to obtain the graphene and manganese dioxide nano composite material.
The mass percentage of the concentrated sulfuric acid in the step (1) is 98%.
The potassium permanganate is added gradually in the step (1) within 20-50 min.
The mass percent of the graphite oxide in the graphite oxide dispersion liquid in the step (2) is 1-3%.
The solid content of the graphene dispersion liquid in the step (3) is 2-5 g/L.
The acid in the step (3) is concentrated hydrochloric acid or concentrated sulfuric acid.
The ultrasonic power in the step (3) is 150-1000W.
The graphene and manganese dioxide nanocomposite material in the step (3) is in a petal shape or a rod shape.
The vacuum drying temperature in the step (3) is 80-120 ℃, and the time is 12-24 h.
By changing the proportion of the graphene and the potassium permanganate, manganese dioxide and graphene nano composite materials with different manganese dioxide loading amounts can be obtained.
Advantageous effects
(1) The preparation method is simple and easy to operate, needs few chemical drugs, has low cost, simple and easy reaction control, has no pollution to the environment, does not need expensive equipment, and is suitable for industrial production;
(2) The petal-shaped or rod-shaped manganese dioxide nanocrystalline has larger specific surface area, and the reaction area of active substances is enlarged; the graphene can be used as an efficient carrier, so that the use efficiency of manganese dioxide is improved, and agglomeration is prevented; when the material is used as an electrode material, the internal resistance of the electrode can be greatly reduced, so that electrons can be smoothly transferred in the material, and the performance of the composite material is greatly improved;
(3) The graphene and manganese dioxide nanocomposite prepared by the invention has good application prospects in the fields of chemical catalysis, environmental management, biosensing, energy storage and the like.
Drawings
FIG. 1 is a scanning electron microscope image of field emission scanning of loaded valvular manganese dioxide nanocrystals onto graphene;
FIG. 2 is a scanning electron microscope image of field emission scanning with rod-like manganese dioxide nanocrystals loaded on graphene;
FIG. 3 is an X-ray diffraction pattern of a graphene and manganese dioxide nanocomposite;
FIG. 4 shows a graphene and petal-shaped manganese dioxide nanocrystalline composite electrode in 1MLi 2 SO 4 Voltammogram of rectangular character in solution at a scan rate of 1 mV/s.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
1g of graphite, 0.75g of sodium nitrate and 23ml of 98wt.% sulfuric acid are fully stirred and mixed uniformly in an ice-water bath, and 3g of potassium permanganate is gradually added within 0.5 h; then reacting for 40min in a water bath at 35 ℃; adding 46ml of deionized water at room temperature, stirring for 15min, and finally adding 140ml of deionized water and 10ml of hydrogen peroxide; and repeatedly filtering and washing the obtained product until the product is neutral to obtain the graphite oxide. Dispersing 0.1g of graphite oxide into 50ml of water, adding 0.1ml of hydrazine hydrate, refluxing in a water bath at 95 ℃ for 1h, repeatedly filtering and washing the obtained product until the product is neutral, and obtaining the graphene. Then 0.1g of graphene is added into 50ml of deionized water; after ultrasonic dispersion is carried out for 1h, 2.724g of saturated solution of potassium permanganate is added, 3.1g of hydrochloric acid is dripped, and ultrasonic auxiliary reaction is carried out for 3h at 70 ℃; and repeatedly filtering and washing the obtained product until the product is neutral, and performing vacuum drying for 24 hours at the temperature of 80 ℃ to obtain the graphene and manganese dioxide nano composite material. The manganese dioxide nanocrystalline prepared under the condition is petal-shaped (see figure 1), the crystal structure of the manganese dioxide nanocrystalline is alpha-type manganese dioxide (see figure 3), and the loading capacity of the manganese dioxide nanocrystalline is 50.8wt.%.
Example 2
1g of graphite, 0.75g of sodium nitrate and 23ml of 98wt.% sulfuric acid are fully stirred and mixed uniformly in an ice-water bath, and 3g of potassium permanganate is gradually added within 0.5 h; then reacting for 20min in a water bath at 35 ℃; adding 46ml of deionized water at room temperature, stirring for 15min, and finally adding 140ml of deionized water and 10ml of hydrogen peroxide; and repeatedly filtering and washing the obtained product until the product is neutral to obtain the graphite oxide. Dispersing 0.1g of graphite oxide into 50ml of water, adding 0.2ml of hydrazine hydrate, refluxing in a water bath at 95 ℃ for 1h, repeatedly filtering and washing the obtained product until the product is neutral, and obtaining the graphene. Then 0.1g of graphene is added into 50ml of deionized water; after ultrasonic dispersion is carried out for 2 hours, 1.816g of saturated solution of potassium permanganate is added, 2.06g of hydrochloric acid is dripped, and ultrasonic auxiliary reaction is carried out for 2 hours at 70 ℃; and repeatedly filtering and washing the obtained product until the product is neutral, and performing vacuum drying for 24 hours at the temperature of 80 ℃ to obtain the graphene and manganese dioxide nano composite material. The manganese dioxide nanocrystalline prepared under the condition is petal-shaped, the crystal structure of the manganese dioxide nanocrystalline is alpha-type manganese dioxide, and the loading capacity of the manganese dioxide nanocrystalline is 48.7wt.%.
Example 3
1g of graphite, 0.75g of sodium nitrate and 23ml of 98wt.% sulfuric acid are fully stirred and mixed uniformly in an ice-water bath, and 3g of potassium permanganate is gradually added within 0.5 h; then reacting for 40min in a water bath at 35 ℃; adding 46ml of deionized water at room temperature, stirring for 15min, and finally adding 140ml of deionized water and 10ml of hydrogen peroxide; and repeatedly filtering and washing the obtained product until the product is neutral to obtain the graphite oxide. Dispersing 0.1g of graphite oxide into 50ml of water, adding 0.3ml of hydrazine hydrate, refluxing in a water bath at 95 ℃ for 1h, repeatedly filtering and washing the obtained product until the product is neutral, and obtaining the graphene. Then 0.1g of graphene is added into 50ml of deionized water; after ultrasonic dispersion for 3 hours, adding 1.008g of saturated solution of potassium permanganate, dropwise adding 1g of hydrochloric acid, and performing ultrasonic auxiliary reaction for 4 hours at 70 ℃; and repeatedly filtering and washing the obtained product until the product is neutral, and performing vacuum drying for 24 hours at the temperature of 80 ℃ to obtain the graphene and manganese dioxide nano composite material. The manganese dioxide nanocrystalline prepared under the condition is rod-shaped (see figure 2), the crystal structure of the manganese dioxide nanocrystalline is alpha-type manganese dioxide, and the loading capacity of the manganese dioxide nanocrystalline is 42.9wt.%.
Example 4
1g of graphite, 0.9g of sodium nitrate and 27ml of 98wt.% sulfuric acid are fully stirred and mixed uniformly in an ice-water bath, and 4g of potassium permanganate is gradually added within 0.5 h; then reacting for 40min in a water bath at 35 ℃; adding 46ml of deionized water at room temperature, stirring for 15min, and finally adding 140ml of deionized water and 10ml of hydrogen peroxide; and repeatedly filtering and washing the obtained product until the product is neutral to obtain the graphite oxide. Dispersing 0.1g of graphite oxide into 50ml of water, adding 0.1ml of hydrazine hydrate, refluxing in a water bath at 95 ℃ for 1h, repeatedly filtering and washing the obtained product until the product is neutral, and obtaining the graphene. Then 0.1g of graphene is added into 50ml of deionized water; after ultrasonic dispersion is carried out for 1h, 2.724g of saturated solution of potassium permanganate is added, 3.1g of hydrochloric acid is dripped, and ultrasonic auxiliary reaction is carried out for 2h at 70 ℃; and repeatedly filtering and washing the obtained product until the product is neutral, and performing vacuum drying for 24 hours at the temperature of 80 ℃ to obtain the graphene and manganese dioxide nano composite material. The manganese dioxide nanocrystalline prepared under the condition is petal-shaped, the crystal structure of the manganese dioxide nanocrystalline is alpha-type manganese dioxide, and the loading capacity of the manganese dioxide nanocrystalline is 47.3wt.%. Weighing 0.5g of composite material, fully grinding the composite material in a ball mill, adding 10 percent of acetylene black and 8 percent of polytetrafluoroethylene emulsion, mixing the mixture into paste, uniformly coating the paste on foamed nickel, drying the foamed nickel at 80 ℃, and preparing an electrode under the pressure of 10 MPa; with Pt electrode as counter electrode and Ag/AgCl as reference electrode, 1MLi 2 SO 4 The aqueous solution is electrolyte to form a three-electrode system. The composite electrode is scanned at 1mV/sAt rate, voltammograms which exhibit a rectangular profile (see FIG. 4). The specific capacitance value measured at a scan rate of 1mV/s is about 440F/g; after 1000 cycles at a scan rate of 5mV/s, the specific capacitance value does not decay by more than 10%.
Example 5
1g of graphite, 0.9g of sodium nitrate and 27ml of 98wt.% sulfuric acid are fully stirred and mixed uniformly in an ice water bath, and 4g of potassium permanganate is gradually added within 0.5 h; then reacting for 30min in a water bath at 35 ℃; adding 46ml of deionized water at room temperature, stirring for 15min, and finally adding 140ml of deionized water and 15ml of hydrogen peroxide; and repeatedly filtering and washing the obtained product until the product is neutral to obtain the graphite oxide. Dispersing 0.1g of graphite oxide into 50ml of water, adding 0.2ml of hydrazine hydrate, refluxing for 1 hour in a water bath at 95 ℃, and repeatedly filtering and washing the obtained product until the product is neutral to obtain graphene. Then 0.1g of graphene is added into 50ml of deionized water; after ultrasonic dispersion is carried out for 1h, 1.816g of saturated solution of potassium permanganate is added, 2.06g of hydrochloric acid is dripped, and ultrasonic auxiliary reaction is carried out for 5h at 70 ℃; and repeatedly filtering and washing the obtained product until the product is neutral, and performing vacuum drying at 120 ℃ for 12 hours to obtain the graphene and manganese dioxide nano composite material. The manganese dioxide nanocrystalline prepared under the condition is rod-shaped, the crystal structure of the manganese dioxide nanocrystalline is alpha-type manganese dioxide, and the loading capacity of the manganese dioxide nanocrystalline is 45.5wt.%. 0.1g of the composite material was weighed out, 10mL of 30% H was measured 2 O 2 The materials are sequentially added into 100mL of methylene blue dye solution with the concentration of 10mg/L, a catalytic degradation experiment is carried out under constant-speed stirring, and after 60min, the degradation rate of the methylene blue is 63.5%.
Example 6
1g of graphite, 1g of sodium nitrate and 30ml of 98wt.% sulfuric acid are fully stirred and uniformly mixed in an ice-water bath, and 5g of potassium permanganate is gradually added within 0.5 h; then reacting for 40min in a water bath at 35 ℃; adding 46ml of deionized water at room temperature, stirring for 15min, and finally adding 140ml of deionized water and 18ml of hydrogen peroxide; and repeatedly filtering and washing the obtained product until the product is neutral to obtain the graphite oxide. Dispersing 0.1g of graphite oxide into 50ml of water, adding 0.3ml of hydrazine hydrate, refluxing in a water bath at 95 ℃ for 1h, repeatedly filtering and washing the obtained product until the product is neutral to obtain graphiteAn alkene. Then 0.1g of graphene is added into 50ml of deionized water; after ultrasonic dispersion for 1h, adding 1.008g of saturated solution of potassium permanganate, dropwise adding 1g of hydrochloric acid, and performing ultrasonic auxiliary reaction for 3h at 70 ℃; and repeatedly filtering and washing the obtained product until the product is neutral, and performing vacuum drying for 24 hours at the temperature of 80 ℃ to obtain the graphene and manganese dioxide nano composite material. The manganese dioxide nanocrystalline prepared under the condition is rod-shaped, the crystal structure of the manganese dioxide nanocrystalline is alpha-type manganese dioxide, and the loading capacity of the manganese dioxide nanocrystalline is 40.7wt.%. Weighing 5g of composite material and 60mg of oxidant chlorine dioxide, placing the composite material and the oxidant chlorine dioxide into 100ml of waste water containing a dyeing agent naphthol green, wherein COD in the waste water Cr 1481mg/L, and measuring COD in the wastewater after 30min of catalytic oxidation Cr The removal rate reaches 71 percent, the decolorization rate is 97 percent, and good catalytic activity, COD (chemical oxygen demand) are still maintained after 9 times of cyclic use Cr The removal rate can still reach 68 percent.
Example 7
1g of graphite, 1g of sodium nitrate and 30ml of 98wt.% sulfuric acid are fully stirred and mixed uniformly in an ice water bath, and 5g of potassium permanganate is gradually added within 0.5 h; then reacting for 40min in a water bath at 35 ℃; adding 46ml of deionized water at room temperature, stirring for 15min, and finally adding 140ml of deionized water and 18ml of hydrogen peroxide; and repeatedly filtering and washing the obtained product until the product is neutral to obtain the graphite oxide. Dispersing 0.1g of graphite oxide into 50ml of water, adding 0.1ml of hydrazine hydrate, refluxing for 1 hour in a water bath at 95 ℃, and repeatedly filtering and washing the obtained product until the product is neutral to obtain graphene. Then 0.1g of graphene is added into 50ml of deionized water; after 3 hours of ultrasonic dispersion, adding 2.724g of saturated solution of potassium permanganate, dropwise adding 3.1g of hydrochloric acid, and carrying out ultrasonic auxiliary reaction for 3 hours at 70 ℃; and repeatedly filtering and washing the obtained product until the product is neutral, and performing vacuum drying for 24 hours at the temperature of 80 ℃ to obtain the graphene and manganese dioxide nano composite material. The manganese dioxide nanocrystalline prepared under the condition is petal-shaped, the crystal structure of the manganese dioxide nanocrystalline is alpha-type manganese dioxide, and the loading capacity of the manganese dioxide nanocrystalline is 49.3wt.%. Weighing 0.5g of composite material, fully grinding the composite material in a ball mill, adding 10% of acetylene black and 8% of polytetrafluoroethylene emulsion, preparing the mixture into paste, uniformly coating the paste on copper foil to be used as a lithium ion battery cathode material, and obtaining the reversible specific capacity of 400mAh/g through charge and discharge tests under the current density of 100mAh/g and the reversible specific capacity of 310mAh/g after 100 cycles.
Example 8
1g of graphite, 1g of sodium nitrate and 40ml of 98wt.% sulfuric acid are fully stirred and uniformly mixed in an ice-water bath, and 5g of potassium permanganate is gradually added within 0.5 h; then reacting for 40min in a water bath at 35 ℃; adding 46ml of deionized water at room temperature, stirring for 15min, and finally adding 140ml of deionized water and 30ml of hydrogen peroxide; and repeatedly filtering and washing the obtained product until the product is neutral to obtain the graphite oxide. Dispersing 0.1g of graphite oxide into 50ml of water, adding 0.2ml of hydrazine hydrate, refluxing in a water bath at 95 ℃ for 1h, repeatedly filtering and washing the obtained product until the product is neutral, and obtaining the graphene. Then 0.1g of graphene is added into 50ml of deionized water; after ultrasonic dispersion is carried out for 1h, 1.816g of saturated solution of potassium permanganate is added, 2.06g of hydrochloric acid is dripped, and ultrasonic auxiliary reaction is carried out for 4h at 70 ℃; and repeatedly filtering and washing the obtained product until the product is neutral, and performing vacuum drying for 24 hours at the temperature of 80 ℃ to obtain the graphene and manganese dioxide nano composite material. The manganese dioxide nanocrystalline prepared under the condition is rod-shaped, the crystal structure of the manganese dioxide nanocrystalline is alpha-type manganese dioxide, and the loading capacity of the manganese dioxide nanocrystalline is 44.3wt.%. 0.5g of the composite material was weighed into 50ml of 44mg/m 3 After sealing for 12 hours, the removal rate of formaldehyde was found to be 87.2%.
Claims (9)
1. A preparation method of a graphene and manganese dioxide nanocomposite material comprises the following steps:
(1) Stirring and mixing graphite, potassium nitrate and concentrated sulfuric acid uniformly in an ice water bath, adding potassium permanganate with the mass ratio of 1-5: 1 to the graphite, reacting for 20-40 min at 30-40 ℃, adding deionized water with the volume-mass ratio of 100-200 ml: 1g to the graphite at room temperature, reacting for 15-30 min, adding hydrogen peroxide with the volume-mass ratio of 10-30 ml: 1g to the graphite, and filtering and washing the obtained product to be neutral to obtain graphite oxide; wherein the volume-to-volume ratio of the concentrated sulfuric acid to the graphite is 20-40 ml: 1g, and the mass-to-volume ratio of the potassium nitrate to the concentrated sulfuric acid is 20-50 g: 1L;
(2) Dispersing the graphite oxide in water to obtain graphite oxide dispersion liquid, adding hydrazine hydrate, wherein the volume mass ratio of the hydrazine hydrate to the graphite oxide is 1-3 ml: 1g, reacting at 95 ℃ for 1-24 h, and washing a product to be neutral to obtain graphene;
(3) Ultrasonically dispersing the graphene in a saturated potassium permanganate solution according to the mass ratio of 10-30: 1 to obtain a graphene dispersion solution, adding acid with the molar ratio of 2-5: 1 to potassium permanganate, carrying out ultrasonic auxiliary reaction at the temperature of 60-80 ℃ for 1-5 h, carrying out suction filtration and washing on the obtained product until the product is neutral, and carrying out vacuum drying to obtain the graphene and manganese dioxide nano composite material.
2. The method for preparing the graphene and manganese dioxide nanocomposite material according to claim 1, wherein the method comprises the following steps: the mass percentage of the concentrated sulfuric acid in the step (1) is 98%.
3. The method for preparing the graphene and manganese dioxide nanocomposite material according to claim 1, wherein the method comprises the following steps: the potassium permanganate is added gradually in the step (1) within 20-50 min.
4. The method for preparing the graphene and manganese dioxide nanocomposite material according to claim 1, wherein the method comprises the following steps: the mass percent of the graphite oxide in the graphite oxide dispersion liquid in the step (2) is 1-3%.
5. The method for preparing the graphene and manganese dioxide nanocomposite material according to claim 1, wherein the method comprises the following steps: the solid content of the graphene dispersion liquid in the step (3) is 2-5 g/L.
6. The method for preparing the graphene and manganese dioxide nanocomposite material according to claim 1, wherein the method comprises the following steps: the acid in the step (3) is concentrated hydrochloric acid or concentrated sulfuric acid.
7. The method for preparing the graphene and manganese dioxide nanocomposite material according to claim 1, wherein the method comprises the following steps: the ultrasonic power in the step (3) is 150-1000W.
8. The method for preparing the graphene and manganese dioxide nanocomposite material according to claim 1, wherein the method comprises the following steps: the graphene and manganese dioxide nanocomposite material in the step (3) is petal-shaped or rod-shaped.
9. The method for preparing the graphene and manganese dioxide nanocomposite material according to claim 1, wherein the method comprises the following steps: the vacuum drying temperature in the step (3) is 80-120 ℃, and the time is 12-24 h.
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| CN109183750B (en) * | 2018-07-30 | 2020-09-08 | 盐城德正机械有限公司 | Oil absorption equipment |
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