CN112441580B - Graphite oxide powder, method for the production thereof and use thereof - Google Patents
Graphite oxide powder, method for the production thereof and use thereof Download PDFInfo
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- CN112441580B CN112441580B CN201910799704.2A CN201910799704A CN112441580B CN 112441580 B CN112441580 B CN 112441580B CN 201910799704 A CN201910799704 A CN 201910799704A CN 112441580 B CN112441580 B CN 112441580B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/23—Oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention provides a graphite oxide, a preparation method thereof, a film containing the graphite oxide and application thereof in the field of sea water desalination. The interlayer spacing of the graphite oxide is controlled by adjusting the oxidation condition of the graphite, so that the water molecules can pass through the interlayer spacing of the trapped ions at the same time, and the requirements of seawater desalination are met. The graphite oxide has good hydrophilicity and antibacterial property, and is suitable for the field of sea water desalination.
Description
Technical Field
The invention relates to the field of graphite materials, in particular to graphite oxide powder and a preparation method thereof, a film containing the graphite oxide powder, and application of the graphite oxide powder and the film in the field of sea water desalination.
Background
The earth water resources are rich, but the fresh water resources only account for 3 percent of the total amount of the earth water, wherein the surface water only accounts for 0.3 percent of the total amount of the fresh water, and the problem of shortage of the water resources which can be developed and utilized by human beings has become the fact of being out of the contest with the annual increase of the water demand. In order to utilize seawater resources, seawater desalination is a major problem facing humans.
The key step of sea water desalination is desalination, and the most difficult to remove of various salts are various monovalent ions, and their diameter is usually less than 10 -3 Micron. Sea water desalination most commonly used at presentThe method is to filter out dissolved ions in seawater through RO membranes. There are however also problems with RO membranes in use due to the materials used. Because RO membrane material does not possess antibacterial property, it easily takes place membrane pollution, has to change regularly, brings a great deal of inconvenience for the user, has increased use cost. Meanwhile, due to the hydrophobicity of the membrane material, high pressure is needed in order to maintain high water flux in use, so that the problems of high working pressure, low treatment rate and high energy consumption exist. Therefore, in order to achieve efficient desalination of sea water, it is necessary to develop a new material having excellent properties such as antibacterial property and hydrophilicity.
One of the directions of research that has been recently being pursued is to produce graphene by a redox method. Graphite oxide and graphene, which are carbon materials, have excellent antibacterial properties, which have been confirmed by many studies. In particular, graphite oxide has strong hydrophilicity due to a large amount of oxygen-containing groups. The original interlayer spacing of the graphite can be increased by a severe oxidation method in the preparation process of the graphite oxide, namely the interlayer spacing is increased from 0.34nm to about 0.9nm, which is a basic and common method for stripping the graphite into graphene and is one of means for forming desalting and water permeable channels. Many examples of the application of graphite oxide in water treatment have also emerged in recent years. For example, in the document Yue-Heng Xi, et al, graphic-based membranes with uniform 2D nanochannels for precise sieving of mono-/multi-value metal ions.volume 550, (2018): 208-218, graphite oxide was prepared into a film, and its removal effect on various ions was studied. The result shows that the membrane can realize interception of ions with the radius of hydrated ions being larger than 0.8nm, but can not realize interception of K + 、Na + 、Li + And (3) removing the equivalent monovalent metal ions.
In order to remove dissolved ions in seawater, particularly monovalent metal ions having a small hydrated ion radius, it is required to control the interlayer spacing of graphite oxide to 0.6nm or less. Numerous efforts have been made to adjust the interlayer spacing of graphite oxide. For example, patent document CN105214607a, in which the interlayer spacing of graphite is adjusted by introducing an intercalator, reduced graphene oxide of a layered porous nanostructure is prepared in the interlayer spacing range of 0.413 to 0.89nm, and is used in the field of wastewater treatment. In patent CN108137415a, an integral film of integrated highly oriented halogenated graphene is prepared by introducing halogen on the graphene surface, the spacing of the multiple halide planes in the integral layer being 0.35-1.2nm. In patent CN103693637a, an interlayer material is interposed between graphene layers of a graphene laminate to obtain an expanded graphite containing an interlayer material, and XRD test results show that the expanded graphite has diffraction peaks in the range of 18 ° to 24 ° in 2θ, and the interlayer spacing of the expanded graphite is 0.37 to 0.49nm as calculated by bragg equation. However, the techniques disclosed in the above patent documents all achieve the purpose of controlling the interlayer spacing by introducing a new group or intercalation agent between the layers of graphite, and the obtained substance is not a simple graphite oxide, so that in the application of sea water desalination, the water permeability is low due to the poor hydrophilicity, the applied water pressure is high, and the treatment efficiency is low due to the high energy consumption.
In addition, in patent document CN106882801a, graphene oxide having different interlayer spacing is produced by controlling the degree of reduction. Because the center part of the graphene oxide is highly oxidized, and the reduction process is gradually carried out from the edge of the graphene oxide to the center, the obtained graphene oxide has poor hydrophilicity at the edge, water molecules are not easy to pass through, and the graphene oxide cannot be applied to the field of water treatment.
Disclosure of Invention
In view of the above prior art, an object of the present invention is to provide an oxide powder of graphite which can pass water molecules between layers while entrapping monovalent metal ions, and a method for preparing the same, and also to provide a film having high water-passing property, antibacterial property and filterability, which comprises the oxide powder of graphite.
The present invention provides a graphite oxide powder, wherein the graphite oxide has an interlayer spacing of 0.4nm or more and 0.6nm or less, and the oxygen atom concentration of the inner edge part of a single sheet of the graphite oxide is 5% to 64% higher than that of the central part.
The oxide powder of graphite has a graphite-like layered structure, which can specifically trap monovalent metal ions by having an interlayer spacing of 0.4nm or more and <0.6 nm. The interlayer spacing can be obtained by reading the (002) peak diffraction angle of the oxide powder of graphite through XRD curve and calculating through Bragg equation.
In order to clarify the characteristics of the graphite oxide powder of the present invention, it is necessary to define specific positions of the edge portion and the center portion. According to the optical microscope characterization, the oxides of the graphite of the present invention are mostly irregular, and the maximum sheet diameter and the minimum sheet diameter are relatively close. The graphite oxide of the present invention is defined as follows in terms of its center and edge portions: the center part is the area of the longest sheet diameter of the graphite oxide sheet, the midpoint position of the longest sheet diameter is less than 10% of the longest sheet diameter, and the edge part is the area of the longest sheet diameter of the graphite oxide sheet, the boundary of which is less than 10% of the longest sheet diameter.
The oxygen atom concentration at the edge portion and the center portion in a single sheet of the graphite oxide of the present invention can be measured by the following method: and (3) respectively measuring the atomic percentages of oxygen and carbon elements on the oxide surface of the graphite by adopting high-precision EDX, and representing the concentration of oxygen atoms by the ratio of the oxygen atoms to the total atoms. According to the invention, the oxygen atom concentration of the inner edge part of a single piece of the oxide of the graphite is 5-64% higher than that of the central part, and more hydrophilic groups can be introduced, so that the hydrophilicity of the inner edge part of the single piece of the oxide of the graphite is improved, the entry of water molecules is facilitated, meanwhile, the hydrophobicity of the central part is reserved, and the rapid removal of the water molecules is facilitated, so that a rapid channel structure of the water molecules is formed, and the high water passing rate can be realized without the need of externally adding high water pressure.
The graphite oxide in the present invention may be of any size. In order to achieve an effective application effect, the volume of the portion of the effective layer spacing is maximized, and the size of the graphite oxide is preferably 2000 mesh or less, and more preferably 500 mesh or less. In order to ensure consistent oxidation levels for each sheet of graphite oxide, a narrow size distribution of graphite oxide, i.e., an oxide of graphite having a D90 to D10 difference of less than 20 microns, is preferred.
In the present invention, in terms of adjusting the interlayer spacing of the graphite oxide, it is preferable that the graphite oxide has an oxygen-carbon atomic ratio of 0.38 to 0.46 at the edge portion and an oxygen-carbon atomic ratio of 0.28 to 0.36 at the center portion in a single sheet. When the oxygen-carbon atomic ratio of the central portion and the edge portion is too low, the oxidation of the oxide of graphite tends to be insufficient, resulting in too small an interlayer spacing, thereby deteriorating the water passing property. When the oxygen-carbon atomic ratio is too high, the oxide of graphite tends to be excessively oxidized, resulting in an excessively large interlayer spacing, and thus monovalent metal ions cannot be trapped.
In the present invention, it is preferable that the specific surface area of the graphite oxide powder is 15 to 150m in terms of controlling the oxidation degree of the graphite oxide and further adjusting the interlayer spacing 2 And/g. When the specific surface area is within the above range, the excessive oxidation caused by the excessively high specific surface area can be avoided, and the interlayer spacing is excessively large, so that monovalent metal ions cannot be trapped; meanwhile, the insufficient surface oxidation caused by the excessively low specific surface area is avoided, the interlayer spacing is excessively small, and the water trafficability is damaged.
The graphite oxide of the invention maintains the ordered structure of the graphite to a certain extent, and can be specifically obtained by the method of Raman spectrum I D /I G Characterization. In the present invention, the Raman spectrum I of the graphite oxide is preferable D /I G 0.6-0.9. The reason for this is I D /I G Too high a value indicates that too much defect is introduced by the oxidation, while too low a value indicates that the structure is closer to the original structure of graphite.
The graphite oxide powder of the invention can be obtained by introducing oxygen-containing groups into the edge part of graphite by adopting an oxidation method milder than the traditional oxidation method, so as to realize partial oxidation of graphite, thereby leading the obtained graphite oxide to have the interlayer spacing more than or equal to 0.4nm and less than 0.6 nm. Specifically, the method comprises the following steps:
step (1): adding 100-180 parts by mass of concentrated sulfuric acid into 1 part by mass of graphite under the ice water bath condition, and mixing for 5-20 minutes to realize the partial intercalation of the concentrated sulfuric acid into graphite layers;
step (2): adding 1.5-2 parts by mass of potassium permanganate, heating to 20-45 ℃, and keeping for 1-2 hours;
step (3): dropwise adding 150-250 parts by mass of deionized water, and then adding 10-20 parts by mass of hydrogen peroxide;
step (4): repeatedly washing and drying the product obtained in the step (3) to obtain the graphite oxide powder.
In order to control the oxidation degree of the oxide of the graphite, both the oxidation of the edge region of the graphite and the increase of the interlayer spacing caused by the excessive oxidation of the central region are ensured, the amount of concentrated sulfuric acid in the step (1) is preferably 110 to 170 parts by mass, more preferably 120 to 160 parts by mass, the amount of potassium permanganate in the step (2) is preferably 1.6 to 1.8 parts by mass, more preferably 1.65 to 1.75 parts by mass, the amount of deionized water in the step (3) is preferably 150 to 220 parts by mass, and the amount of hydrogen peroxide is preferably 13 to 18 parts by mass, relative to 1 part by mass of the graphite. The washing of the product in the step (4) can be realized by a filtering or centrifuging method, and the drying can be realized by vacuum drying or freeze drying.
The graphite oxide powder of the invention can realize the effect of removing monovalent ions with smaller radius of hydrated ions in the application of sea water desalination through the specific structure. Accordingly, the present invention also provides a film comprising the graphite oxide powder and a binder as described above. The binder may be any conventional binder, and one of polyvinylidene fluoride, epoxy resin, sodium carboxymethyl cellulose, styrene-butadiene rubber is preferable in view of applicable cost. The film forming method may be vacuum filtration, blade coating, leveling, spin coating, among which blade coating is preferable for improving the water permeability of the film.
According to the present invention, the graphite oxide powder and the film comprising the graphite oxide powder and the binder can be applied to the field of sea water desalination.
Advantageous effects
The graphite oxide provided by the invention has the interlayer spacing more than or equal to 0.4nm and less than 0.6nm, which is lower than that of the traditional graphite oxide, so that the removal of monovalent ions in the seawater is possible. On the other hand, the edges of the graphite oxide have good hydrophilicity due to the presence of a large number of oxygen-containing groups at the edges. And the oxidation degree of the relative center part is low, and the water is hydrophobic, so that the water entering the oxide layers of the graphite can be rapidly discharged. The oxide of graphite having this structure can efficiently achieve the desalting effect on seawater. In addition, the oxide of the graphite maintains the antibacterial property of the graphite oxide, and can effectively improve the pollution resistance. Therefore, the graphite oxide overcomes a plurality of problems of RO membranes and is suitable for application in the field of sea water desalination.
The preparation method of the graphite oxide provided by the invention is different from the traditional preparation method of graphite oxide, avoids dangerous high-temperature reaction, has milder and safer reaction conditions, and is easier to realize industrialized mass production.
Drawings
FIG. 1 is an electron micrograph of a single piece of the graphite oxide powder obtained in example 3.
FIG. 2 is an optical micrograph of a single plate of the graphite oxide powder obtained in example 3.
Fig. 3 is an XRD curve of the oxide powder of graphite obtained in example 2.
Detailed Description
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples.
The specific chemicals and suppliers involved in the present invention:
high-purity natural graphite: 150 mesh, 325 mesh, 500 mesh, purchased from Qingdao Tianhe and Dahi graphite limited.
Concentrated sulfuric acid (98%, AR), potassium permanganate (AR), hydrogen peroxide (30%, AR), purchased from national pharmaceutical group chemical reagent Co., ltd.).
Polyvinylidene fluoride: HSV-900, available from Aroma China.
The performance characterization method according to the present invention is as follows.
A. Characterization of graphite oxide powder:
(A-1) interlayer spacing
The oxide powders of the graphite of examples and comparative examples were subjected to diffraction angle measurement by an X-ray diffractometer (XRD, bruker D8 ADVANCE Da Vinci) under conditions of a tube voltage of 40kV and a tube current of 150mA, scanning rate of 5 DEG/min, and (002) interlayer spacing of the oxide of graphite was calculated by Bragg equation.
(A-2) oxygen atom concentration
The oxide powders of the graphite of examples and comparative examples were characterized for surface morphology using an electron microscope (SEM, irises 4800) and the edge/center positions thereof were determined. The ratio of oxygen atoms to carbon atoms at the center and edge portions of the monolithic graphite oxide, respectively, was determined using a high-precision EDX accessory, and the oxygen atom concentration was characterized as the ratio of oxygen atoms to the total number of atoms. The calculation method of the oxygen atom concentration difference is [ (edge portion-center portion)/center portion ] ×100%. (A-3) specific surface area
The specific surface area of the oxide powders of the graphite of examples and comparative examples was measured by using a nitrogen adsorber (BEL Japan Belsorp ii mini).
(A-4) Raman Spectroscopy I D /I G
The Raman spectra of the graphite oxide powders of examples and comparative examples were measured by using a Raman spectrometer (inVia qntir), and the peak intensity ratio I of the D peak and the G peak was calculated D /I G 。
B. The characteristic parameters of the film comprising graphite oxide powder and binder were tested as follows:
(B-1) brine filtration rate and salt removal Rate
An aqueous solution of 20wt% NaCl was used as the salt solution. The filtrate produced per unit filtration time was collected by passing brine through the membrane between the surfaces of the graphite oxide film and the brine in a direction parallel to the flow direction of the brine at a vacuum degree of 0.09MPa by vacuum filtration, and the volume of the filtrate and the salt concentration were measured. The volume of the filtrate divided by the filtration time is the filtration rate of the brine. The salt content trapped by the membrane can be simply calculated through the salt content in the filtrate, and the salt removal rate can be obtained by dividing the salt content in the original brine.
(B-2) antibacterial Properties
The graphite oxide film was tested for its antimicrobial properties, and the characterization standard was ISO2073:2013, test strain Escherichia coli ATCC 8739, concentration 2.5 x 10 5 CFU/mL, incubation time 24hr, test method: plate count method. The antibacterial property is characterized by an antibacterial value, and when the antibacterial value is more than 3, the antibacterial property is good.
The results of the above tests are shown in Table 1 below and FIGS. 1-3.
< preparation of oxide powder of graphite >
Example 1
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.5g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): repeatedly washing the product obtained in the step (3) until the pH value is 7, and freeze-drying to obtain graphite oxide powder.
Example 2
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1 hour;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Since the oxide of this graphite is oxidized to a lower degree than conventional graphite oxide, the XRD curve of this product exhibits diffraction peaks in the vicinity of 2θ=20° in addition to diffraction peaks in the vicinity of 2θ=10°.
Example 3
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Electron micrographs show that the graphite oxide maintains the morphology of the natural graphite material and that the edge portions are whitened over the center portions due to poor conductivity due to high oxidation.
Optical micrographs show that the oxides of graphite are irregularly shaped with the largest and smallest sheet diameters being relatively close.
Example 4
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 2 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 5
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 2g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 6
Step (1): 140g of concentrated sulfuric acid is added into 1g of 325 mesh natural graphite under the ice water bath condition, and the mixture is mixed for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 7
Step (1): 180g of concentrated sulfuric acid is added into 1g of 325 mesh natural graphite under the ice water bath condition, and the mixture is mixed for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 8
Step (1): adding 100g of concentrated sulfuric acid into 1g of 500-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 9
Step (1): adding 100g of concentrated sulfuric acid into 1g of 150-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 10
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 5 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 11
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 20 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 12
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), controlling the temperature to 20 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 13
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 45 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 14
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 150g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 15
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 250g of deionized water into the mixture obtained in the step (2), and then adding 15g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 16
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 10g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Example 17
Step (1): adding 100g of concentrated sulfuric acid into 1g of 325-mesh natural graphite under the ice water bath condition, and mixing for 10 minutes;
step (2): adding 1.65g of potassium permanganate into the mixture obtained in the step (1), heating to 35 ℃, and mixing for 1.5 hours;
step (3): dropwise adding 200g of deionized water into the mixture obtained in the step (2), and then adding 20g of hydrogen peroxide;
step (4): the product was repeatedly washed until pH 7 and freeze-dried to obtain graphite oxide powder.
Comparative example 1
Step (1): under the ice water bath condition, sequentially adding 22ml of concentrated sulfuric acid, 0.35g of sodium nitrate and 2.1g of potassium permanganate into 1g of natural graphite with 500 meshes, and mixing for 1 hour;
step (2): heating the mixture obtained in the step (1) to 35 ℃ for reaction for 4 hours;
step (3): adding 50g of deionized water into the mixture obtained in the step (2), and heating to 90 ℃ to react for 15 minutes;
step (4): adding 60g of deionized water and 5g of hydrogen peroxide into the mixture obtained in the step (3), and reacting for 5 minutes to obtain a product;
step (5): repeatedly washing the product until the pH value is 7, and freeze-drying to obtain graphite oxide.
< preparation of oxide film of graphite >
The graphite oxide powders obtained in examples 1 to 17 or the graphite oxide powder obtained in comparative example 1 were thoroughly mixed with 10 parts by mass of a 10wt% polyvinylidene fluoride/NMP solution, and a wet film was prepared by a knife coating method, and the wet film was dried at 80℃for 2 hours to obtain a film of graphite oxide.
Claims (6)
1. An oxide powder of graphite, characterized in that: the oxide of the graphite has a particle size of 0.4nm or more<An interlayer spacing of 0.6nm, and an oxygen atom concentration at an edge portion thereof is 5% to 64% higher than that at a central portion in the single sheet of the oxide of the graphite, an oxygen-carbon atom ratio at an edge portion thereof is 0.38 to 0.46, an oxygen-carbon atom ratio at a central portion thereof is 0.28 to 0.36, and a specific surface area of the oxide powder of the graphite is 15 to 150m 2 And/g, wherein the center part is a region with the distance between the longest sheet diameters of the graphite oxide sheets being less than 10% of the longest sheet diameters, and the edge part is a region with the distance between the longest sheet diameters of the graphite oxide sheets being less than 10% of the boundaries of the longest sheet diameters.
2. The graphite oxide powder of claim 1, wherein: i of the Raman spectrum of the oxide of graphite D /I G 0.6-0.9.
3. A method for preparing the graphite oxide powder of claim 1 or 2, comprising the steps of:
step (1): adding 100-180 parts by mass of concentrated sulfuric acid into 1 part by mass of graphite under the ice water bath condition, and mixing for 5-20 minutes to realize the partial intercalation of the concentrated sulfuric acid into graphite layers;
step (2): adding 1.5-2 parts by mass of potassium permanganate, heating to 20-45 ℃, and keeping for 1-2 hours;
step (3): dropwise adding 150-250 parts by mass of deionized water, and then adding 10-20 parts by mass of hydrogen peroxide;
step (4): and (3) repeatedly washing and drying the product obtained in the step (3) to obtain the graphite oxide powder.
4. A film, characterized in that: the film comprises the graphite oxide powder of claim 1 or 2 and a binder.
5. Use of the graphite oxide powder of claim 1 or 2 in the field of desalination of sea water.
6. Use of the membrane of claim 4 in the field of desalination of sea water.
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