CN112479304B - Porous material with functional graphene oxide film on surface, and preparation method and application thereof - Google Patents
Porous material with functional graphene oxide film on surface, and preparation method and application thereof Download PDFInfo
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Abstract
A preparation method of a porous material with a functional graphene oxide film on the surface comprises the following steps: and (3) immersing the porous material into the graphene oxide dispersion liquid for a period of time, taking out the solution, draining, and drying to obtain the porous material with the functional graphene oxide film on the surface. The preparation process of the method does not need special equipment, cleaning and hydrophilic treatment, and is easy for industrial production; the silicate type materials such as red bricks and concrete blocks are fully utilized, and the silicate type materials have the advantages of good hydrophilicity, porous structures and strong adsorbability, so that waste is changed into wealth, the surface area of the graphene oxide material contacted with sewage is greatly increased, and the photocatalytic efficiency is improved.
Description
Technical Field
The invention belongs to the field of inorganic functional materials. In particular to a porous material with a functional graphene oxide film on the surface, a preparation method and application thereof.
Background
Since the human society enters industrial civilization, the problem of environmental pollution is becoming serious. Environmental pollution which adversely affects human health mainly includes air pollution, water pollution, soil pollution and the like. Water is the source of life, and the treatment of water pollution is also the key point in environmental treatment. At present, the photocatalysis technology is widely used for treating water pollution. The principle of treating water pollution by photocatalysis is as follows: the photocatalyst is irradiated by sunlight to induce and generate a plurality of active ingredients such as hydroxyl free radicals, superoxide free radicals and the like, and the active ingredients can synergistically degrade organic pollutants in the polluted water body, so that the problems of eutrophication of the polluted water body and overhigh chemical oxygen demand are solved, and the purpose of purifying the polluted water body is achieved.
Graphene is a new material with wide applications, and in recent years, graphene composite materials are also used in the field of sewage treatment. The graphene material has good electronic transmission performance, and can be combined with a photocatalytic material in the process of photocatalytic degradation of organic pollutants in water, and the graphene material can be used as an adsorbent and an electron acceptor in the photocatalytic process, so that the degradation efficiency of organic matters and heavy metal pollutants in the photocatalytic sewage treatment process can be greatly improved.
However, the existing graphene composite material for water treatment has the defects of high cost, difficulty in large-scale industrial production and the like.
Disclosure of Invention
In order to improve the prior art, the invention aims to provide a porous material with a functional graphene oxide film on the surface. The invention provides the following technical scheme:
the embodiment of the invention provides a preparation method of a porous material with a functional graphene oxide film on the surface, which comprises the following steps: and (3) immersing the porous material into the graphene oxide dispersion liquid for a period of time, taking out the solution, draining, and drying to obtain the porous material with the functional graphene oxide film on the surface.
According to an embodiment of the present invention, for example, the graphene oxide dispersion is prepared by:
(a) adding high-purity crystalline flake graphite and sodium nitrate into concentrated sulfuric acid, refrigerating to 0 ℃, stirring all the time, and keeping the temperature at 0 ℃ for a period of time;
(b) slowly adding potassium permanganate, keeping the temperature at 0-5 ℃ in the potassium permanganate adding process, and continuously stirring for a period of time;
(c) heating to 30-50 deg.C, and stirring for a while;
(d) stopping heating and continuing stirring, slowly adding a certain amount of deionized water, and controlling the temperature of the system to be below 90 ℃;
(e) adding a certain amount of 30% hydrogen peroxide under the condition that the temperature of the system is controlled to be not higher than 80 ℃, stirring for 5-20 minutes, and taking out;
(f) washing and separating graphene oxide, and then, adding metered pure water to prepare a graphene oxide dispersion liquid with a certain concentration by measuring the content of the graphene oxide in water;
preferably, the size of the high-purity crystalline flake graphite is 200 meshes-1200 meshes, preferably 200 meshes-1000 meshes, more preferably 300 meshes-1000 meshes, more preferably 400 meshes-800 meshes;
preferably, the incubation period in step (a) is >1h, preferably >2 h; preferably, the heat preservation time in the step (a) is 1h-5h, preferably 2h-4 h;
preferably, the system temperature in step (d) is controlled at 70 ℃ to 90 ℃, preferably at 75 ℃ to 85 ℃, more preferably at 77 ℃ to 82 ℃, and most preferably at 80 ℃;
preferably, the washed graphene oxide in step (f) is: repeatedly washing the graphene oxide with deionized water until the graphene oxide is neutral;
preferably, the purity of the high-purity flake graphite is >95%, preferably > 97%, preferably > 98%;
preferably, in the step (a), the mass ratio of the high-purity crystalline flake graphite to the sodium nitrate is 1:0.5-1.5, preferably 1:0.8-1.2, preferably 1: 1;
preferably, in the step (a), the using amount ratio of the high-purity crystalline flake graphite to the concentrated sulfuric acid is 1g (30-80mL), preferably 1g (40-60mL), preferably 1g:50 mL;
preferably, the mass of the potassium permanganate in the step (b) is 3 to 10 times, preferably 4 to 8 times, and preferably 6 times that of the high-purity flake graphite in the step (a);
preferably, the stirring in step (a) is continued for 30-120min, preferably 60-100min, preferably 90 min;
preferably, the stirring is continued for a period of time in step (c) of from 1 to 3 hours, preferably 2 hours.
Preferably, the volume ratio of the deionized water in the step (d) to the concentrated sulfuric acid in the step (a) is (0.6-1.0):1, preferably 0.8: 1;
preferably, the volume ratio of the 30% hydrogen peroxide in the step (e) to the concentrated sulfuric acid in the step (a) is (0.05-0.2):1, preferably 0.1: 1;
preferably, step (c) is: heating to 40 ℃, and continuing stirring for a period of time;
preferably, step (e) is: adding a certain amount of 30 percent hydrogen peroxide under the condition that the temperature of the system is controlled to be not higher than 80 ℃, stirring for 10 minutes, and taking out.
According to one embodiment of the invention, for example, the porous material comprises at least one of the following materials: building waste, volcanic rock, natural zeolite; preferably, the construction waste comprises red bricks and concrete blocks; preferably, the porous material is crushed to a size of 10-40 mm; preferably, the size of the porous material is 15-25mm, and the pore diameter of the porous material is 500nm-5 μm; preferably, the composition of the graphene oxide dispersion liquid is as follows: the graphene oxide has the sheet diameter of 400-1200 nm, the single-layer rate of more than 90%, the purity of the graphene oxide of more than 99%, the dispersion liquid is pure water, the concentration of the graphene oxide is 5mg/mL, and the graphene oxide does not contain any non-graphene oxide substances such as a dispersing agent and the like; the forbidden band width is 1.71-5.0 eV, and the corresponding intrinsic absorption wavelength limit is 245-725 nm;
preferably, the step of immersing the porous material into the graphene oxide dispersion liquid for a period of time is: immersing the porous material in the graphene oxide dispersion for 2 seconds to 10 seconds, preferably for 5 seconds to 10 seconds, and most preferably for 5 seconds;
preferably, the drying is carried out in a forced air drying oven at 50-70 ℃ for 2-4 h.
The embodiment of the invention also provides a porous material with the functional graphene oxide film on the surface, and the porous material with the functional graphene oxide film on the surface is prepared by the method.
According to an embodiment of the present invention, for example, the porous material having the functional graphene oxide thin film on the surface thereof includes a porous material as a support and a functional graphene oxide thin film attached to the surface of the support.
According to one embodiment of the invention, for example, the porous material comprises at least one of the following materials: building waste, volcanic rock, natural zeolite;
preferably, the construction waste comprises red bricks and concrete blocks;
preferably, the porous material is crushed to a size of 10-40 mm;
preferably, the size of the porous material is 15-25mm, and the pore diameter of the porous material is 500nm-5 μm.
Embodiments of the present invention also provide a water purification application of the porous material having the functional graphene oxide thin film on the surface, which includes: and (3) putting the porous material with the functional graphene oxide film on the surface into polluted water, and standing for a period of time under the irradiation of outdoor natural light.
According to one embodiment of the invention, for example, the period of time is greater than or equal to 24 hours; preferably, the period of time is greater than or equal to 48 hours; preferably, the period of time is greater than or equal to 72 hours; preferably, the period of time is greater than or equal to 96 hours;
preferably, the mass ratio of the polluted water body to the porous material with the surface provided with the functional graphene oxide film is 10: 0.5 to 10: 5, preferably 10: 1 to 10: 3, most preferably 10: 2.
according to one embodiment of the invention, for example, the contaminated body of water is a static body of water.
According to one embodiment of the invention, for example, the contaminated body of water is a body of flowing water.
Drawings
FIG. 1 is a schematic illustration of a product static process for treating contaminated water in accordance with an embodiment of the present invention;
FIG. 2 is a schematic diagram of a product dynamic process for treating contaminated water according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of the operation process of preparing a graphene oxide coating film by the spin coating method in comparative example 1 of the present invention.
Description of reference numerals: 1-water; 2-red brick particles; 3-a sewage tank; 4-water flow direction; 5-a peristaltic pump; 6-sewage level.
Detailed Description
The electroluminescent materials and devices according to the invention will be further described with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Example 1 impregnation method for preparing porous material with functional graphene oxide film on surface
1000g of red brick particles are immersed in 500mL of graphene oxide dispersion liquid with the concentration of 5mg/mL for 5 seconds, and the solution is taken out and drained and naturally dried at room temperature and marked as # 1.
The preparation process of the 5mg/mL graphene oxide dispersion liquid is as follows:
(1) adding 2g of 500-mesh high-purity crystalline flake graphite and 2g of sodium nitrate into 100mL of concentrated sulfuric acid, refrigerating to 0 ℃, stirring all the time, and keeping the temperature at 0 ℃ for 2 hours;
(2) slowly adding 12g of potassium permanganate, keeping the temperature at 0-5 ℃ in the potassium permanganate adding process, and continuously stirring for 90 minutes;
(3) heating to 40 ℃, and continuing stirring for 2 hours;
(4) stopping heating and continuing stirring, slowly adding 80mL of deionized water, and controlling the temperature of the system at 80 ℃;
(5) adding 10mL of hydrogen peroxide with the mass fraction of 30% under the condition of controlling the temperature of the system to be not more than 80 ℃, stirring for 10 minutes, and taking out;
(6) and repeatedly washing the obtained graphene oxide with deionized water to be neutral and separating, and then determining the content of the graphene oxide in water, and adding metered pure water to prepare graphene oxide dispersion liquid with the concentration of 5 mg/mL.
The graphene oxide dispersion liquid is characterized by means such as an atomic force microscope, an SEM (scanning electron microscope), a TEM (transmission electron microscope), an EDS (electron-dispersive spectroscopy), a Raman spectrum and a UV-Vis (ultraviolet and visible light) spectrum, and the graphene oxide dispersion liquid comprises the following components: the graphene oxide has the sheet diameter of 400-1200 nm, the single-layer rate of more than 90%, the purity of the graphene oxide of more than 99%, the dispersion liquid is pure water, the concentration of the graphene oxide is 5mg/mL, and the graphene oxide does not contain any non-graphene substances such as a dispersing agent; the forbidden band width is 1.71-5.0 eV, and the corresponding intrinsic absorption wavelength limit is 245-725 nm, i.e. the wide absorption is in the ultraviolet and visible light range.
Red brick particles: the method mainly comprises the steps of carrying out secondary processing on red brick garbage for construction sold in the market into small particles, wherein the size is 10-40mm, the main size is controlled to be 15-25mm, the pore diameter mainly depends on the original pore diameter of the red brick sold in the market of the original product, and the effect is better on various light porous materials with high porosity, such as natural volcanic rock, natural zeolite and the like; the aperture is within the range of 500nm-5 μm, and the water purification effect is better.
Example 2
1000g of red brick particles were immersed in 500mL of the graphene oxide dispersion (same as in example 1) for 5 seconds, and the solution was drained and dried in a forced air drying oven at 50 ℃ for 2 hours and recorded as # 2.
Example 3
1000g of red brick particles were immersed in 500mL of the graphene oxide dispersion (same as in example 1) for 5 seconds, and the solution was drained and dried in a forced air drying oven at 70 ℃ for 2 hours, which was designated as # 3.
Example 4
Immersing 1000g of red brick particles into 500mL of graphene oxide dispersion (same as in example 1) for 2 seconds, taking out the solution, draining, and naturally drying at room temperature to mark as 41 #; and continuously taking 1000g of red brick particles, immersing the red brick particles into the rest graphene oxide dispersion liquid for 2 seconds, taking out the drained solution, and naturally drying at room temperature and marking the drained solution as 42 #.
Example 5
1000g of red brick particles were immersed in 500mL of graphene oxide dispersion (same as in example 1) for 2 seconds, the solution was drained and dried in a forced air drying oven at 70 ℃ for 2h, labeled # 51; and continuously taking 1000g of red brick particles, immersing the red brick particles into the rest graphene oxide dispersion liquid for 2 seconds, taking out the draining solution, and drying the red brick particles in a forced air drying oven at 70 ℃ for 2 hours and marking the dried red brick particles as 52 #.
The preparation method of the above embodiments 1 to 5 has the following technical advantages:
(1) no special equipment is needed in the preparation process;
(2) no cleaning and hydrophilic treatment are needed;
(3) the silicate materials such as red bricks and concrete blocks are fully utilized, and the silicate materials have the advantages of good hydrophilicity, porous structure and strong adsorbability, so that waste is turned into wealth, the contact surface area of the graphene oxide material and sewage is greatly increased, and the photocatalytic efficiency is improved;
(4) because small particle materials such as red bricks, concrete blocks and the like have good adsorbability, the formed graphene oxide film has good adhesiveness, does not need special heat treatment, and can be dried naturally or by hot air at 70 ℃;
(5) the process flow is beneficial to large-scale industrial production;
(6) the waste is recycled and is functionally recycled, and the waste is converted into treasure.
EXAMPLE 6 Water purification (static method)
The products of the embodiments 1-5 can be widely used for purifying water quality of shallow water type artificial wetlands, artificial floating islands and the like, and the adsorption characteristic of the porous material is fully utilized, and the photocatalytic characteristic of the graphene oxide material is added, so that the photodecomposition of various pollutants in water is further promoted, and the purpose of efficiently purifying the water quality is achieved.
The river sewage with certain serious eutrophication is turbid and has more algae, and the water quality indexes of the part of the river sewage are as follows: pH6.34, TDS (Total dissolved solids) 227mg/L, conductivity 454. mu.S/cm, oxidation-reduction potential (ORP)207mV, Chemical Oxygen Demand (COD)54.35 mg/L. The water is classified according to COD index of GB3838-2002 'surface water environmental quality standard', and belongs to surface inferior V-class water. 1000mL of the wastewater was placed in a beaker, and 200g of the coated red brick granules obtained in examples 1 to 5 were placed in the beaker, and the water quality index was measured after the beaker was left standing for 24 hours, 48 hours, and 72 hours under outdoor natural light irradiation. The experimental method is shown in the attached figure 1. The change in COD (unit: mg/L) is shown in the following table.
TABLE 1 static Water purification test results
| Sample number | Untreated |
1# | 2# | 3# | 41# | 42# | 51# | 52# |
| 0h | 54.35 | 54.35 | 54.35 | 54.35 | 54.35 | 54.35 | 54.35 | 54.35 |
| 24h | 44.45 | 21.68 | 20.26 | 20.10 | 20.87 | 21.45 | 20.56 | 20.96 |
| 48h | 43.20 | 16.56 | 15.42 | 15.28 | 16.36 | 16.48 | 15.72 | 15.89 |
| 72h | 43.10 | 15.78 | 15.20 | 14.89 | 15.08 | 15.20 | 14.89 | 14.68 |
From the above test results, the following conclusions can be drawn:
(1) the untreated red brick particles can purify water to a certain degree, but only have the adsorption effect, and the water purification degree is limited due to factors such as adsorption capacity and the like;
(2) the water quality purification performance of the red brick particles subjected to graphene oxide film coating treatment in the embodiments 1-5 is greatly improved, the inferior V-type sewage can be purified to surface IV water after 24h natural illumination, and the inferior V-type sewage can reach the surface III-type water standard after 48h (according to the regulations of surface water environmental quality standard GB3838-2002, the Chemical Oxygen Demand (COD) of the I-type water and the II-type water should be less than or equal to 15; the COD of the III-type water should be less than or equal to 20; the COD of the IV-type water should be less than or equal to 30; and the COD of the V-type water should be less than or equal to 40);
(3) the conditions for purifying the water quality are only air and sunlight, other energy sources and chemical reagents are not needed, the operation is simple, and the energy sources are saved;
(4) the process of purifying water quality by using the products of the above examples 1-5 is not simple flocculation and adsorption, and the adsorption flocculation is only the secondary transfer of pollutants and does not eliminate the pollution; the embodiment of the invention fully utilizes the adsorption characteristic of the porous material to enrich high pollutants, then exerts the photocatalysis characteristic of the modified graphene oxide, decomposes the pollutants into water and carbon dioxide, and thoroughly eliminates the pollution.
EXAMPLE 7 Water purification (dynamic method)
The river sewage with certain serious eutrophication is turbid and has more algae, and the water quality indexes of the part of the river sewage are as follows: pH6.34, Total Dissolved Solids (TDS)227mg/L, conductivity 454. mu.S/cm, Oxidation-reduction potential (ORP)207mV, Chemical Oxygen Demand (COD)54.35 mg/L. The water is classified according to COD index of GB3838-2002 'surface water environmental quality standard', and belongs to surface inferior V-class water. 1000mL of the wastewater was placed in a beaker, 200g of one of the coated red brick granules of examples 3-5 was placed in another beaker, then a peristaltic pump (power: 50%) was turned on, and the liquid was circulated to the red brick granules, which were placed under outdoor natural light for 24 hours and 48 hours before testing the water quality index. The experimental method is shown in the attached figure 1. The change in COD (unit: mg/L) is shown in the following table. In the above experiment, the mass ratio of the sewage to the red brick particles was 10: 2, the using amount can be determined according to the fund for treating the polluted water body in practical application, for example, as less as 10: 0.5, 10: 1 can obtain effective treatment effect, and the effective treatment effect is as high as 10: 3. 10: 5 the effect is better.
TABLE 2 dynamic Water purification test results
| Sample number | Untreated |
3# | 42# | 52# |
| 0h | 54.35 | 54.35 | 54.35 | 54.35 |
| 24h | 48.77 | 30.22 | 31.67 | 30.65 |
| 48h | 47.42 | 25.43 | 24.54 | 25.34 |
From the above test results, the following conclusions can be drawn:
(1) the untreated red brick particles can purify water to a certain degree under static conditions, and the performance under dynamic conditions is greatly reduced;
(2) the red brick particles subjected to graphene oxide film coating treatment in the embodiments 3-5 of the invention have excellent water quality purification performance under a static condition, can better exert the water quality purification performance under a dynamic condition, can purify inferior V-class sewage to surface V-class water after 24h natural illumination, and reaches the surface IV-class water standard after 48 h;
(3) the product of the embodiment of the invention only has the conditions of air and sunlight for purifying water quality, does not need other energy sources and chemical reagents, is simple to operate and saves energy sources;
(4) the red brick particles subjected to the graphene oxide coating treatment can purify water in a static environment and can also purify flowing water such as rivers.
Comparative example 1 spin coating method for preparing graphene oxide coating film
This comparative example used the same graphene oxide dispersion as example 1.
As shown in fig. 3, the whole modified graphene oxide film is prepared as follows. Firstly, the first step is to
And ultrasonically cleaning the glass sheet substrate in acetone, ethanol and deionized water for 15min, taking out, rinsing with deionized water for three times, and drying with nitrogen. Then adopting the volume ratio of concentrated H 2 SO 4 ：H 2 O 2 The glass sheet substrate was treated at 80 ℃ for 30min with a solution of 7:3, removed, rinsed repeatedly with deionized water, and finally stored in deionized water for future use. And then, the treated glass sheet is subjected to glue spreading and film coating.
The inventor of the application finds that the coating film is more uniform by adopting stepped acceleration for the uniform coating film. In the whole film coating process, the rotating speed, the glue dripping time, the acceleration and the pH value of a dispersion liquid are main factors influencing the quality of a film. And finally, drying the glue homogenizing film at 70 ℃ for 2h, reducing the glue homogenizing film for 2s by using 800W microwaves, and carrying out vacuum heat treatment at 200 ℃ for 2h to obtain the required film.
The spin-coating method can be implemented only on the surface of a planar material and requires special spin-coating machine equipment, the implementation process needs about 10-20 hours, cleaning and hydrophilic treatment are required in the preparation process, subsequent treatment is required for organic solvents and waste acid, large-scale industrial production is difficult to realize, and large-scale production equipment investment is large.
Comparative example 2 preparation of graphene oxide coating film by using pull-up degree film method
Lift coating process
The basic process flow of the dip coating method is consistent with that of the spin coating method, and the method is different from the dip coating machine used in equipment, and has the same other defects and characteristics. The method comprises the following steps:
(1) cleaning and degreasing: firstly, a glass sheet with the specification of 75mm multiplied by 25mm multiplied by 1mm is sequentially placed in acetone, ethanol and deionized water for ultrasonic cleaning for 15min, and is taken out and then washed for 3 times by the deionized water, and is dried by nitrogen.
(2) Hydrophilic treatment: placing the glass sheet in a concentrated H 2 SO 4 Mixing with 30% hydrogen peroxide solution (80 deg.C) at volume ratio of 7:3 for 30min, taking out, repeatedly cleaning with deionized water, and storing in deionized water for use.
(3) Dip-coating and dip-coating: after the pH value of the dispersion liquid containing a certain amount of modified GO is adjusted to 8, a coating interval, a pulling (dipping) rate and coating times are set in a pulling coating machine, the coating process is automatically carried out, a glass sheet substrate firstly runs from the highest point to the lowest point at a set dipping rate at a constant speed, runs from the lowest point to the highest point at the same pulling rate at a constant speed after being dipped for 5s, and carries out the 2 nd-time coating after a certain time interval, and the steps are repeated until the specified times are finished.
(4) Reduction and heat treatment: drying at 70 deg.C for 2h, reducing with 800W microwave for 2s, and vacuum heat treating at 200 deg.C for 2 h.
The draw-down film method also has the same disadvantages as the spin coating method.
The embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (16)
1. A preparation method of a porous material with a functional graphene oxide film on the surface is characterized by comprising the following steps: immersing the porous material into the graphene oxide dispersion liquid for a period of time, taking out the solution, draining, and drying to obtain the porous material with the functional graphene oxide film on the surface;
the graphene oxide dispersion liquid is prepared by the following method:
(a) adding high-purity crystalline flake graphite and sodium nitrate into concentrated sulfuric acid, refrigerating to 0 ℃, stirring all the time, and keeping the temperature at 0 ℃ for a period of time;
(b) slowly adding potassium permanganate, keeping the temperature at 0-5 ℃ in the potassium permanganate adding process, and continuously stirring for a period of time;
(c) heating to 30-50 deg.C, and stirring for a while;
(d) stopping heating and continuing stirring, slowly adding a certain amount of deionized water, and controlling the temperature of the system to be below 90 ℃;
(e) adding a certain amount of 30% hydrogen peroxide under the condition that the temperature of the system is controlled to be not higher than 80 ℃, stirring for 5-20 minutes, and taking out;
(f) washing and separating graphene oxide, and then, adding metered pure water to prepare a graphene oxide dispersion liquid with a certain concentration by measuring the content of the graphene oxide in water;
the size of the high-purity crystalline flake graphite is 200-1200 meshes;
the period of time of the heat preservation in the step (a) is more than 1 h;
the system temperature in the step (d) is controlled at 70-90 ℃;
the washing graphene oxide in the step (f) is as follows: repeatedly washing graphene oxide to neutrality by using deionized water;
the purity of the high-purity crystalline flake graphite is more than 95 percent;
in the step (a), the mass ratio of the high-purity crystalline flake graphite to the sodium nitrate is 1: 0.5-1.5;
in the step (a), the dosage ratio of the high-purity crystalline flake graphite to the concentrated sulfuric acid is 1g (30-80 mL);
the mass of the potassium permanganate in the step (b) is 3-10 times that of the high-purity crystalline flake graphite in the step (a);
the continuous stirring in the step (a) is continuously stirred for 30-120 min;
the continuous stirring in the step (c) for a period of time is continuously stirred for 1-3 h;
the volume ratio of the deionized water to the concentrated sulfuric acid in the step (a) in the step (d) is (0.6-1.0): 1;
the volume ratio of the 30% hydrogen peroxide to the concentrated sulfuric acid in the step (a) is (0.05-0.2): 1;
the porous material comprises at least one of the following materials: building waste, volcanic rock, natural zeolite;
the porous material is crushed into 10-40mm size;
the size of the porous material is 15-25mm, and the pore diameter of the porous material is 500nm-5 mu m;
the graphene oxide dispersion liquid comprises the following components: the graphene oxide has the sheet diameter of 400-1200 nm, the single-layer rate of more than 90%, the purity of the graphene oxide of more than 99%, the dispersion liquid is pure water, the concentration of the graphene oxide is 5mg/mL, and the graphene oxide does not contain any non-graphene substances such as a dispersing agent; the forbidden band width is 1.71-5.0 eV, and the corresponding intrinsic absorption wavelength limit is 245-725 nm;
the porous material is immersed in the graphene oxide dispersion liquid for a period of time as follows: immersing the porous material into the graphene oxide dispersion liquid for 2-10 seconds;
the drying is carried out for 2h-4h at 50-70 ℃ in a forced air drying oven.
2. The method of claim 1, wherein the high purity flake graphite is 200-1000 mesh in size.
3. The method of claim 1, wherein the incubation in step (a) is for a period of time in the range of 1h to 5 h.
4. The method of claim 1, wherein the system temperature in step (d) is controlled at 75-85 ℃.
5. The method according to claim 1, wherein in the step (a), the mass ratio of the high-purity crystalline flake graphite to the sodium nitrate is 1: 0.8-1.2.
6. The method according to claim 1, wherein in step (a), the ratio of the amount of the high-purity crystalline flake graphite to the amount of the concentrated sulfuric acid is 1g (40-60 mL).
7. The method of claim 1, wherein the mass of potassium permanganate in step (b) is 4-8 times that of the high purity flake graphite in step (a).
8. The method of claim 1, wherein the period of continued stirring in step (a) is continued for 60-100 min.
9. The method of claim 1, wherein the period of continued stirring in step (c) is continued for 2 hours.
10. A porous material having a functional graphene oxide thin film on the surface, wherein the porous material having a functional graphene oxide thin film on the surface is prepared by the method of any one of claims 1 to 9.
11. The porous material with the functional graphene oxide film on the surface according to claim 10, wherein the porous material with the functional graphene oxide film on the surface comprises a porous material as a support and a functional graphene oxide film attached to the surface of the support.
12. The porous material with the surface provided with the functional graphene oxide film according to claim 11, wherein the porous material comprises at least one of the following materials: building waste, volcanic rock, natural zeolite;
the porous material is crushed into 10-40mm size;
the size of the porous material is 15-25mm, and the pore diameter of the porous material is 500nm-5 μm.
13. The water purification application of the porous material with the surface provided with the functional graphene oxide film according to any one of claims 10 to 12, wherein the porous material with the surface provided with the functional graphene oxide film is put into polluted water and is placed for a period of time under outdoor natural light irradiation.
14. The water purification application of claim 13, wherein the period of time is greater than or equal to 24 hours;
the mass ratio of the polluted water body to the porous material with the surface provided with the functional graphene oxide film is 10: 0.5 to 10: 5.
15. the water purification application of claim 13 or 14, wherein the contaminated body of water is a static body of water.
16. The water purification application of claim 13 or 14, wherein the contaminated body of water is a body of flowing water.
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