CN110026171B - Preparation method of efficient graphene-based photocatalytic material - Google Patents
Preparation method of efficient graphene-based photocatalytic material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 150
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 47
- 239000010936 titanium Substances 0.000 claims abstract description 47
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 43
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 43
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 38
- 238000010926 purge Methods 0.000 claims abstract description 34
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012153 distilled water Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 19
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 19
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 19
- 238000004821 distillation Methods 0.000 claims abstract description 18
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000007603 infrared drying Methods 0.000 claims abstract description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 33
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 30
- 229920002125 Sokalan® Polymers 0.000 abstract description 24
- 239000004584 polyacrylic acid Substances 0.000 abstract description 24
- 239000004408 titanium dioxide Substances 0.000 abstract description 13
- 239000011941 photocatalyst Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
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- -1 polypropylene Polymers 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
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- 238000011156 evaluation Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
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- 238000004887 air purification Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
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- 230000008023 solidification Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/39—
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a high-efficiency graphene-based photocatalytic material, which comprises the following steps: adding two-dimensional graphene into distilled water, then uniformly stirring ascorbic acid to obtain a graphene turbid liquid; adding acrylic acid into the graphene suspension, then carrying out low-temperature ultrasonic reaction for 2-4h, carrying out water bath reaction for 2-6h, and carrying out reduced pressure distillation reaction for 2-4h to obtain coated three-dimensional graphene; adding tetrabutyl titanate into absolute ethyl alcohol, adding ethyl cellulose, and stirring until the ethyl cellulose is completely dissolved to form a titanium liquid; putting the three-dimensional graphene with the coating into a titanium liquid, performing low-temperature ultrasonic reaction for 2-4h, taking out, and quickly drying to obtain the three-dimensional graphene with the titanium film; and (3) placing the three-dimensional graphene with the titanium film into an infrared drying box to be dried for 2-4h at constant temperature, and sintering for 1-2h at constant temperature after nitrogen purging to obtain the graphene-based photocatalytic material. The invention solves the problem that the existing photocatalytic material is easy to dissipate in water, and the titanium dioxide is adhered to the three-dimensional graphene by utilizing the ethyl cellulose and the polyacrylic acid.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a high-efficiency graphene-based photocatalytic material.
Background
In recent 20 years, with the rapid development of economy in China, the development, utilization scale and speed of lake resources are greatly enhanced, the natural evolution process of lakes is influenced, and the ecological system of lakes is seriously damaged. With the rapid development of the social economy and the urbanization process of China, the problem of lake water environment pollution is increasingly prominent. According to the national water resource comprehensive planning evaluation result, the evaluation results of 84 representative lakes across the country show that: 44 lakes are eutrophicated all the year round, accounting for 52.4% of the total number of the lakes to be evaluated, and the rest lakes are in medium-nutrient state. Lake protection and pollution treatment become the key points of environmental protection in China, pollution source control is increased, and the pollution and ecological environment deterioration are restrained to a certain extent, but according to national economic development and future planning, the pollution and degradation situations of lakes are not optimistic.
At present, the application of graphene photocatalysis technology to sewage treatment is a research hotspot, the pollution treatment principle is to recover self-purification of water by using visible light, natural light is the only light source, a power device is not needed, and chemical reagents or biological strains are not needed. However, the mode of putting the graphene photocatalyst is the bottleneck of the current sewage treatment. The graphene photocatalytic net is mainly adopted for treating sewage in rivers or lakes currently, namely the graphene photocatalytic net is formed by taking polypropylene fibers as a base material and loading a plurality of layers of graphene photocatalysts through a unique coating process, can be used for water body purification, air purification and the like, is particularly suitable for treating urban black and odorous water bodies, can decompose toxic organic matters in the water bodies, deodorize and increase the oxygen content of the water bodies, has strong compatibility with other treatment technologies, is green and environment-friendly in material, and can be recycled. However, the photocatalytic material of the existing graphene photocatalyst is not strongly bonded with graphene, so that the photocatalytic material is easily lost in water, and the overall treatment efficiency is reduced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a high-efficiency graphene-based photocatalytic material, which solves the problem that the existing photocatalytic material is easy to dissipate in water, and adopts ethyl cellulose and polyacrylic acid as adhesives to adhere titanium dioxide to three-dimensional graphene, so that the adhesion is effectively improved, surface bonding is formed in the sintering process, and a stable curing effect is formed.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of a high-efficiency graphene-based photocatalytic material comprises the following steps:
step 1, adding two-dimensional graphene into distilled water, and then uniformly stirring ascorbic acid to obtain a graphene suspension;
step 2, adding acrylic acid into the graphene suspension, then carrying out low-temperature ultrasonic reaction for 2-4h, carrying out water bath reaction for 2-6h, and carrying out reduced pressure distillation reaction for 2-4h to obtain coated three-dimensional graphene;
step 3, adding tetrabutyl titanate into absolute ethyl alcohol, adding ethyl cellulose, and stirring until the ethyl cellulose is completely dissolved to form a titanium liquid;
step 4, putting the three-dimensional graphene with the coating into a titanium liquid for low-temperature ultrasonic reaction for 2-4h, taking out and quickly drying to obtain the three-dimensional graphene with the titanium film;
and 5, placing the three-dimensional graphene with the titanium film into an infrared drying box to be dried for 2-4h at constant temperature, and sintering for 1-2h at constant temperature after nitrogen purging to obtain the graphene-based photocatalytic material.
The concentration of the two-dimensional graphene in the distilled water in the step 1 is 5-10g/L, the addition amount of the ascorbic acid is 900% of the mass of the two-dimensional graphene, and the stirring speed for uniformly stirring is 800r/min and 300-.
The addition amount of the acrylic acid in the step 2 is 150% of the mass of the graphene, the temperature of the low-temperature ultrasonic reaction is 5-10 ℃, the ultrasonic frequency is 40-100kHz, the temperature of the water bath reaction is 90-100 ℃, the pressure of the reduced pressure distillation reaction is 60-70% of the atmospheric pressure, and the temperature is 100-120 ℃.
Adding isopropanol at the same time of adding the acrylic acid in the step 2, wherein the adding amount of the isopropanol is 20-40% of the mass of the acrylic acid.
The concentration of the n-butyl titanate in the step 3 in the absolute ethanol is 100-200g/L, the adding amount of the ethyl cellulose is 40-60% of the mass of the n-butyl titanate, and the stirring speed is 1000-2000 r/min.
The mass ratio of the three-dimensional graphene with the coating in the step 4 to the n-butyl titanate in the titanium liquid is 2:10-200, the temperature of the low-temperature ultrasonic reaction is 2-8 ℃, the ultrasonic frequency is 100-200kHz, and the drying temperature is 100-110 ℃.
The temperature of the constant-temperature drying in the step 5 is 180-220 ℃, the humidity is 30-50%, the purging speed of the nitrogen purging is 100-200mL/min, the purging time is 30-100min, and the temperature of the constant-temperature sintering is 300-350 ℃.
Step 1, adding two-dimensional graphene into distilled water, then adding ascorbic acid, and stirring to form a graphene turbid liquid.
Step 2, adding acrylic acid into the graphene turbid liquid, wherein the acrylic acid can be dissolved in distilled water; the graphene with a porous three-dimensional structure can be peeled from the two-dimensional graphene through the low-temperature ultrasonic reaction and the ascorbic acid, and meanwhile, the polypropylene can be rapidly dispersed into the porous three-dimensional structure of the graphene through the high frequency of the ultrasonic reaction, so that a good permeation effect is formed, and the polypropylene is uniformly distributed on the large specific surface area of the graphene, so that a stable liquid film structure can be formed; the water bath reaction can promote the acrylic acid in the graphene to carry out polymerization reaction to obtain polyacrylic acid, and the polyacrylic acid is uniformly distributed in the distilled water and forms an adhesive liquid film on the surface of the graphene; the reduced pressure distillation reaction can evaporate and remove the distilled water as the dissolved solution to obtain the three-dimensional graphene with the surface containing the polyacrylic acid liquid film, and the graphene is doped with a small amount of distilled water adsorbed in the polyacrylic acid.
The isopropanol is used as a molecular weight regulator, can not only make the molecular weight distribution small and narrow, but also has the functions of reducing viscosity and removing reaction heat. Meanwhile, the boiling point of the isopropanol is 82-83 ℃, gas is formed in the water bath reaction process, and the polyacrylic acid in the reaction system is polymerized, so that the isopropanol can be quickly removed while promoting the reaction, and the subsequent reaction is not influenced.
Step 3, adding tetrabutyl titanate into absolute ethyl alcohol to form dissolution and dispersion, then adding ethyl cellulose to form a dispersion system, wherein the ethyl cellulose has good solubility in the absolute ethyl alcohol, can form dissolution in the ethyl alcohol, and can be dispersed to the surface of the tetrabutyl titanate to form a wrapping system; because the content of the ethyl cellulose is less than that of the n-butyl titanate, the ethyl cellulose can only form a semi-wrapping system, and the titanium alcohol liquid with uniformly dispersed n-butyl titanate is obtained.
And 4, adding the three-dimensional graphene with the polyacrylic acid liquid film into the titanium liquid, forming secondary dissolution of the liquid film by utilizing the solubility of polyacrylic acid in absolute ethyl alcohol, uniformly adhering n-butyl titanate on the surface of the three-dimensional graphene based on the co-solubility of polyacrylic acid and ethyl cellulose to form a good film, and drying to obtain the three-dimensional graphene taking polyacrylic acid and ethyl cellulose as composite adhesives and n-butyl titanate as the film layer.
Step 5, drying the three-dimensional graphene with the titanium film in an infrared drying oven at constant temperature, wherein a certain amount of water vapor is collected in the air, the water absorption performance of polyacrylic acid absorbs water at the beginning of heating, the n-butyl titanate is converted into the nano titanium dioxide, the agglomeration problem of the nano titanium dioxide is solved by the curing performance of the polyacrylic acid and the ethyl cellulose, and the water in the polyacrylic acid gradually runs off along with the rise of the temperature to form a stable polyacrylic acid high molecular compound; removing air containing water vapor by a nitrogen purging mode to form an environment of a nitrogen system and also removing butyl ester generated by the reaction; carry out the constant temperature sintering under nitrogen environment, polyacrylic acid and ethyl cellulose form the decomposition at this temperature to solidify nanometer titanium dioxide on the graphite alkene surface, the temperature at this moment can turn into the anatase with nanometer titanium dioxide simultaneously, and has partial titanium dioxide to turn into the rutile type, because the high heat conductivility of graphite alkene, can guarantee that rutile type nanometer titanium dioxide and anatase titanium dioxide form inside and outside wrong system of connecing, has promoted titanium dioxide's photocatalytic degradation performance greatly.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problem that the existing photocatalytic material is easy to dissipate in water, and the titanium dioxide is adhered to the three-dimensional graphene by using the ethyl cellulose and the polyacrylic acid as the adhesive, so that the adhesion is effectively improved, and the surface bonding is formed in the sintering process to form a stable curing effect.
2. The invention adopts the solubility of absolute ethyl alcohol to polyacrylic acid, n-butyl titanate and ethyl cellulose, can ensure the rearrangement of the n-butyl titanate on the surface of the graphene, and forms a surface film taking the polyacrylic acid and the ethyl cellulose as adhesion main bodies.
3. According to the invention, the water vapor in the air is utilized to hydrolyze the n-butyl titanate to form titanium dioxide, and the solidification effects of the ethyl cellulose and the polyacrylic acid are utilized to prevent the aggregation of the nano titanium dioxide, so that the problem of the agglomeration of the titanium dioxide is solved.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
A preparation method of a high-efficiency graphene-based photocatalytic material comprises the following steps:
step 1, adding two-dimensional graphene into distilled water, and then uniformly stirring ascorbic acid to obtain a graphene suspension;
step 2, adding acrylic acid into the graphene suspension, then carrying out low-temperature ultrasonic reaction for 2 hours, carrying out water bath reaction for 2 hours, and carrying out reduced pressure distillation reaction for 2 hours to obtain the three-dimensional graphene with the coating;
step 3, adding tetrabutyl titanate into absolute ethyl alcohol, adding ethyl cellulose, and stirring until the ethyl cellulose is completely dissolved to form a titanium liquid;
step 4, putting the three-dimensional graphene with the coating into a titanium liquid for low-temperature ultrasonic reaction for 2 hours, taking out and quickly drying to obtain the three-dimensional graphene with the titanium film;
and 5, placing the three-dimensional graphene with the titanium film into an infrared drying box to be dried for 2 hours at constant temperature, and sintering for 1-2 hours at constant temperature after nitrogen purging to obtain the graphene-based photocatalytic material.
The concentration of the two-dimensional graphene in the step 1 in distilled water is 5g/L, the addition amount of the ascorbic acid is 300% of the mass of the two-dimensional graphene, and the stirring speed for uniformly stirring is 300 r/min.
The addition amount of the acrylic acid in the step 2 is 100% of the mass of the graphene, the temperature of the low-temperature ultrasonic reaction is 5 ℃, the ultrasonic frequency is 40kHz, the temperature of the water bath reaction is 90 ℃, the pressure of the reduced pressure distillation reaction is 60% of the atmospheric pressure, and the temperature is 100 ℃.
The concentration of the n-butyl titanate in the step 3 in the absolute ethyl alcohol is 100g/L, the adding amount of the ethyl cellulose is 40 percent of the mass of the n-butyl titanate, and the stirring speed is 1000 r/min.
The mass ratio of the three-dimensional graphene with the coating in the step 4 to the n-butyl titanate in the titanium liquid is 2:10, the temperature of the low-temperature ultrasonic reaction is 2 ℃, the ultrasonic frequency is 100kHz, and the drying temperature is 100 ℃.
The temperature of constant-temperature drying in the step 5 is 180 ℃, the humidity is 30%, the purging speed of nitrogen purging is 100mL/min, the purging time is 30min, and the temperature of constant-temperature sintering is 300 ℃.
Example 2
A preparation method of a high-efficiency graphene-based photocatalytic material comprises the following steps:
step 1, adding two-dimensional graphene into distilled water, and then uniformly stirring ascorbic acid to obtain a graphene suspension;
step 2, adding acrylic acid into the graphene turbid liquid, then carrying out low-temperature ultrasonic reaction for 4 hours, carrying out water bath reaction for 6 hours, and carrying out reduced pressure distillation reaction for 4 hours to obtain three-dimensional graphene with a coating;
step 3, adding tetrabutyl titanate into absolute ethyl alcohol, adding ethyl cellulose, and stirring until the ethyl cellulose is completely dissolved to form a titanium liquid;
step 4, putting the three-dimensional graphene with the coating into a titanium liquid for low-temperature ultrasonic reaction for 4 hours, taking out and quickly drying to obtain the three-dimensional graphene with the titanium film;
and 5, placing the three-dimensional graphene with the titanium film into an infrared drying box to be dried for 4 hours at constant temperature, and sintering for 2 hours at constant temperature after nitrogen purging to obtain the graphene-based photocatalytic material.
The concentration of the two-dimensional graphene in the step 1 in distilled water is 10g/L, the addition amount of the ascorbic acid is 900% of the mass of the two-dimensional graphene, and the stirring speed for uniformly stirring is 800 r/min.
The addition amount of the acrylic acid in the step 2 is 150% of the mass of the graphene, the temperature of the low-temperature ultrasonic reaction is 10 ℃, the ultrasonic frequency is 100kHz, the temperature of the water bath reaction is 100 ℃, the pressure of the reduced pressure distillation reaction is 70% of the atmospheric pressure, and the temperature is 120 ℃.
The concentration of the n-butyl titanate in the step 3 in the absolute ethyl alcohol is 200g/L, the adding amount of the ethyl cellulose is 60 percent of the mass of the n-butyl titanate, and the stirring speed is 2000 r/min.
The mass ratio of the three-dimensional graphene with the coating in the step 4 to the n-butyl titanate in the titanium liquid is 2:200, the low-temperature ultrasonic reaction temperature is 8 ℃, the ultrasonic frequency is 200kHz, and the drying temperature is 110 ℃.
The temperature of constant-temperature drying in the step 5 is 220 ℃, the humidity is 50%, the purging speed of nitrogen purging is 200mL/min, the purging time is 100min, and the temperature of constant-temperature sintering is 350 ℃.
Example 3
A preparation method of a high-efficiency graphene-based photocatalytic material comprises the following steps:
step 1, adding two-dimensional graphene into distilled water, and then uniformly stirring ascorbic acid to obtain a graphene turbid liquid;
step 2, adding acrylic acid into the graphene turbid liquid, then carrying out low-temperature ultrasonic reaction for 3 hours, carrying out water bath reaction for 4 hours, and carrying out reduced pressure distillation reaction for 3 hours to obtain three-dimensional graphene with a coating;
step 3, adding tetrabutyl titanate into absolute ethyl alcohol, adding ethyl cellulose, and stirring until the ethyl cellulose is completely dissolved to form a titanium liquid;
step 4, putting the three-dimensional graphene with the coating into a titanium liquid for low-temperature ultrasonic reaction for 3 hours, taking out and quickly drying to obtain the three-dimensional graphene with the titanium film;
and 5, placing the three-dimensional graphene with the titanium film into an infrared drying box to be dried for 3 hours at constant temperature, and sintering for 2 hours at constant temperature after nitrogen purging to obtain the graphene-based photocatalytic material.
The concentration of the two-dimensional graphene in the step 1 in distilled water is 8g/L, the addition amount of the ascorbic acid is 600% of the mass of the two-dimensional graphene, and the stirring speed for uniformly stirring is 500 r/min.
The addition amount of the acrylic acid in the step 2 is 130% of the mass of the graphene, the temperature of the low-temperature ultrasonic reaction is 8 ℃, the ultrasonic frequency is 80kHz, the temperature of the water bath reaction is 95 ℃, the pressure of the reduced pressure distillation reaction is 65% of the atmospheric pressure, and the temperature is 110 ℃.
The acrylic acid in the step 2 is added with isopropanol, and the addition amount of the isopropanol is 30% of the mass of the acrylic acid.
The concentration of the n-butyl titanate in the step 3 in the absolute ethyl alcohol is 150g/L, the adding amount of the ethyl cellulose is 50 percent of the mass of the n-butyl titanate, and the stirring speed is 1500 r/min.
The mass ratio of the three-dimensional graphene with the coating in the step 4 to the n-butyl titanate in the titanium liquid is 2:100, the temperature of the low-temperature ultrasonic reaction is 6 ℃, the ultrasonic frequency is 150kHz, and the drying temperature is 105 ℃.
The temperature of constant-temperature drying in the step 5 is 200 ℃, the humidity is 40%, the purging speed of nitrogen purging is 150mL/min, the purging time is 80min, and the temperature of constant-temperature sintering is 330 ℃.
Example 4
A preparation method of a high-efficiency graphene-based photocatalytic material comprises the following steps:
step 1, adding two-dimensional graphene into distilled water, and then uniformly stirring ascorbic acid to obtain a graphene suspension;
step 2, adding acrylic acid and isopropanol into the graphene suspension, then carrying out low-temperature ultrasonic reaction for 2 hours, carrying out water bath reaction for 2 hours, and carrying out reduced pressure distillation reaction for 2 hours to obtain the three-dimensional graphene with the coating;
step 3, adding tetrabutyl titanate into absolute ethyl alcohol, adding ethyl cellulose, and stirring until the ethyl cellulose is completely dissolved to form a titanium liquid;
step 4, putting the three-dimensional graphene with the coating into a titanium liquid for low-temperature ultrasonic reaction for 2 hours, taking out and quickly drying to obtain the three-dimensional graphene with the titanium film;
and 5, placing the three-dimensional graphene with the titanium film into an infrared drying box to be dried for 2 hours at constant temperature, and sintering for 1 hour at constant temperature after nitrogen purging to obtain the graphene-based photocatalytic material.
The concentration of the two-dimensional graphene in the step 1 in distilled water is 5g/L, the addition amount of the ascorbic acid is 300% of the mass of the two-dimensional graphene, and the stirring speed for uniformly stirring is 300 r/min.
The addition amount of the acrylic acid in the step 2 is 100% of the mass of the graphene, the temperature of the low-temperature ultrasonic reaction is 5 ℃, the ultrasonic frequency is 40kHz, the temperature of the water bath reaction is 90 ℃, the pressure of the reduced pressure distillation reaction is 60% of the atmospheric pressure, and the temperature is 100 ℃; the amount of isopropyl alcohol added was 20% by mass of acrylic acid.
The concentration of the n-butyl titanate in the step 3 in the absolute ethyl alcohol is 100g/L, the adding amount of the ethyl cellulose is 40 percent of the mass of the n-butyl titanate, and the stirring speed is 1000 r/min.
The mass ratio of the three-dimensional graphene with the coating in the step 4 to the n-butyl titanate in the titanium liquid is 2:10, the temperature of the low-temperature ultrasonic reaction is 2 ℃, the ultrasonic frequency is 100kHz, and the drying temperature is 100 ℃.
The temperature of constant-temperature drying in the step 5 is 180 ℃, the humidity is 30%, the purging speed of nitrogen purging is 100mL/min, the purging time is 30min, and the temperature of constant-temperature sintering is 300 ℃.
Example 5
A preparation method of a high-efficiency graphene-based photocatalytic material comprises the following steps:
step 1, adding two-dimensional graphene into distilled water, and then uniformly stirring ascorbic acid to obtain a graphene suspension;
step 2, adding acrylic acid and isopropanol into the graphene turbid liquid, then carrying out low-temperature ultrasonic reaction for 4 hours, carrying out water bath reaction for 6 hours, and carrying out reduced pressure distillation reaction for 4 hours to obtain the three-dimensional graphene with the coating;
step 3, adding tetrabutyl titanate into absolute ethyl alcohol, adding ethyl cellulose, and stirring until the ethyl cellulose is completely dissolved to form a titanium liquid;
step 4, putting the three-dimensional graphene with the coating into a titanium liquid for low-temperature ultrasonic reaction for 4 hours, taking out and quickly drying to obtain the three-dimensional graphene with the titanium film;
and 5, placing the three-dimensional graphene with the titanium film into an infrared drying box to be dried for 4 hours at constant temperature, and sintering for 2 hours at constant temperature after nitrogen purging to obtain the graphene-based photocatalytic material.
The concentration of the two-dimensional graphene in the step 1 in distilled water is 10g/L, the adding amount of the ascorbic acid is 900% of the mass of the two-dimensional graphene, and the stirring speed for uniformly stirring is 800 r/min.
The addition amount of the acrylic acid in the step 2 is 150% of the mass of the graphene, the temperature of the low-temperature ultrasonic reaction is 10 ℃, the ultrasonic frequency is 100kHz, the temperature of the water bath reaction is 100 ℃, the pressure of the reduced pressure distillation reaction is 70% of the atmospheric pressure, and the temperature is 120 ℃; the amount of the isopropyl alcohol added was 40% by mass of acrylic acid.
The concentration of the n-butyl titanate in the step 3 in the absolute ethyl alcohol is 200g/L, the adding amount of the ethyl cellulose is 60 percent of the mass of the n-butyl titanate, and the stirring speed is 2000 r/min.
The mass ratio of the three-dimensional graphene with the coating in the step 4 to the n-butyl titanate in the titanium liquid is 2:200, the low-temperature ultrasonic reaction temperature is 8 ℃, the ultrasonic frequency is 200kHz, and the drying temperature is 110 ℃.
The temperature of constant-temperature drying in the step 5 is 220 ℃, the humidity is 50%, the purging speed of nitrogen purging is 200mL/min, the purging time is 100min, and the temperature of constant-temperature sintering is 350 ℃.
Example 6
A preparation method of a high-efficiency graphene-based photocatalytic material comprises the following steps:
step 1, adding two-dimensional graphene into distilled water, and then uniformly stirring ascorbic acid to obtain a graphene suspension;
step 2, adding acrylic acid and isopropanol into the graphene turbid liquid, then carrying out low-temperature ultrasonic reaction for 3 hours, carrying out water bath reaction for 4 hours, and carrying out reduced pressure distillation reaction for 3 hours to obtain the three-dimensional graphene with the coating;
step 3, adding tetrabutyl titanate into absolute ethyl alcohol, adding ethyl cellulose, and stirring until the ethyl cellulose is completely dissolved to form a titanium liquid;
step 4, putting the three-dimensional graphene with the coating into a titanium liquid for low-temperature ultrasonic reaction for 3 hours, taking out and quickly drying to obtain the three-dimensional graphene with the titanium film;
and 5, placing the three-dimensional graphene with the titanium film into an infrared drying box to be dried for 3 hours at constant temperature, and sintering for 1 hour at constant temperature after nitrogen purging to obtain the graphene-based photocatalytic material.
The concentration of the two-dimensional graphene in the step 1 in distilled water is 10g/L, the addition amount of the ascorbic acid is 700% of the mass of the two-dimensional graphene, and the stirring speed for uniformly stirring is 600 r/min.
The addition amount of the acrylic acid in the step 2 is 140% of the mass of the graphene, the temperature of the low-temperature ultrasonic reaction is 5 ℃, the ultrasonic frequency is 80kHz, the temperature of the water bath reaction is 100 ℃, the pressure of the reduced pressure distillation reaction is 65% of the atmospheric pressure, and the temperature is 115 ℃; the amount of the isopropyl alcohol added was 30% by mass of acrylic acid.
The concentration of the n-butyl titanate in the step 3 in the absolute ethyl alcohol is 180g/L, the adding amount of the ethyl cellulose is 50 percent of the mass of the n-butyl titanate, and the stirring speed is 1600 r/min.
The mass ratio of the three-dimensional graphene with the coating in the step 4 to the n-butyl titanate in the titanium liquid is 2:150, the temperature of the low-temperature ultrasonic reaction is 6 ℃, the ultrasonic frequency is 150kHz, and the drying temperature is 105 ℃.
The temperature of constant-temperature drying in the step 5 is 210 ℃, the humidity is 40%, the purging speed of nitrogen purging is 150mL/min, the purging time is 80min, and the temperature of constant-temperature sintering is 330 ℃.
Performance detection
The comparative example employed a commercially available graphene photocatalyst.
The above tests are all carried out according to the national standards in the field of photocatalysis, and the specific national standards are as follows:
GB/T23761-2009 (Performance test method of photocatalytic air purification material)
GB/T23762-2009 (photocatalysis material water solution system purification test method)
GB/T23763-2009 (evaluation of antibacterial property of photocatalytic antibacterial material and product)
GB/T23764-2009 (photocatalytic self-cleaning material performance test method)
In the detection process, in the antibacterial property detection, the examples 1 to 6 all have good antibacterial effect, and after the 100-day distilled water is adopted for washing and soaking, the photocatalytic antibacterial property is basically unchanged and still reaches 99.99%, while the photocatalytic antibacterial property of the graphene photocatalyst in the comparative example is reduced from 99.99% to 87% after the graphene photocatalyst is soaked in the distilled water for a long time; in the self-cleaning detection process, the performances of the examples 1 to 6 are almost unchanged after 100 days of distilled water washing and soaking, while the contact angle of the comparative example is increased from the original 90.3 degrees to 123.1 degrees.
Comparison before and after Pond Water quality treatment (mg/L)
The graphene photocatalyst prepared in example 1 is placed on the surface of a poor V-class pond, and the specific surface area of the placed graphene photocatalyst is 30% of the area of the pond.
In summary, the invention has the following advantages:
1. the invention solves the problem that the existing photocatalytic material is easy to dissipate in water, and the titanium dioxide is adhered to the three-dimensional graphene by using the ethyl cellulose and the polyacrylic acid as the adhesive, so that the adhesion is effectively improved, and the surface bonding is formed in the sintering process to form a stable curing effect.
2. The invention adopts the solubility of absolute ethyl alcohol to polyacrylic acid, tetrabutyl titanate and ethyl cellulose, can ensure the rearrangement of tetrabutyl titanate on the surface of graphene, and forms a surface film taking polyacrylic acid and ethyl cellulose as adhesion main bodies.
3. According to the invention, water vapor in the air is utilized to hydrolyze n-butyl titanate to form titanium dioxide, and the solidification effects of the ethyl cellulose and the polyacrylic acid are utilized to prevent the aggregation of the nano titanium dioxide, so that the problem of the agglomeration of the titanium dioxide is solved.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (1)
1. A preparation method of a high-efficiency graphene-based photocatalytic material is characterized by comprising the following steps: the method comprises the following steps:
step 1, adding two-dimensional graphene into distilled water, then adding ascorbic acid, and uniformly stirring to obtain a graphene suspension;
step 2, adding acrylic acid into the graphene suspension, then carrying out low-temperature ultrasonic reaction for 2-4h, carrying out water bath reaction for 2-6h, and carrying out reduced pressure distillation reaction for 2-4h to obtain coated three-dimensional graphene;
step 3, adding tetrabutyl titanate into absolute ethyl alcohol, adding ethyl cellulose, and stirring until the ethyl cellulose is completely dissolved to form a titanium liquid;
step 4, putting the three-dimensional graphene with the coating into a titanium liquid for low-temperature ultrasonic reaction for 2-4h, taking out and quickly drying to obtain the three-dimensional graphene with the titanium film;
step 5, placing the three-dimensional graphene with the titanium film into an infrared drying box to be dried for 2-4h at constant temperature, and sintering for 1-2h at constant temperature after nitrogen purging to obtain a graphene-based photocatalytic material;
the adding amount of the acrylic acid in the step 2 is 150% of the mass of the graphene, the temperature of the low-temperature ultrasonic reaction is 5-10 ℃, the ultrasonic frequency is 40-100kHz, the temperature of the water bath reaction is 90-100 ℃, the pressure of the reduced pressure distillation reaction is 60-70% of the atmospheric pressure, and the temperature is 100-120 ℃;
adding isopropanol while adding the acrylic acid in the step 2, wherein the addition amount of the isopropanol is 20-40% of the mass of the acrylic acid;
the concentration of the two-dimensional graphene in the distilled water in the step 1 is 5-10g/L, the addition amount of the ascorbic acid is 900% of the mass of the two-dimensional graphene, and the stirring speed for uniformly stirring is 800 r/min;
the concentration of the n-butyl titanate in the step 3 in the absolute ethanol is 100-200g/L, the adding amount of the ethyl cellulose is 40-60% of the mass of the n-butyl titanate, the stirring speed is 1000-2000r/min,
the mass ratio of the three-dimensional graphene with the coating in the step 4 to the n-butyl titanate in the titanium liquid is 2:10-200, the temperature of the low-temperature ultrasonic reaction is 2-8 ℃, the ultrasonic frequency is 100-200kHz, and the drying temperature is 100-110 ℃;
the temperature of the constant-temperature drying in the step 5 is 180-220 ℃, the humidity is 30-50%, the purging speed of the nitrogen purging is 100-200mL/min, the purging time is 30-100min, and the temperature of the constant-temperature sintering is 300-350 ℃.
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