CN110124724B - Preparation method of functionalized graphene quantum dot/titanium dioxide composite material - Google Patents
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002096 quantum dot Substances 0.000 title claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 17
- 239000012498 ultrapure water Substances 0.000 claims abstract description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000000502 dialysis Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
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- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 10
- 238000001354 calcination Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000011056 performance test Methods 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a preparation method of a functionalized graphene quantum dot/titanium dioxide composite material, which comprises the steps of firstly, taking titanium (IV) isopropoxide as a titanium source, taking polyvinylpyrrolidone as a dispersing agent, and dispersing the titanium (IV) tetraisopropoxide in ethylene glycol under an acidic environment to obtain a titanium solution; carrying out solvothermal reaction on the titanium solution at 160-165 ℃ to obtain yellow flower-shaped titanium dioxide; calcining the yellow titanium dioxide to obtain flower-shaped titanium dioxide; and ultrasonically dispersing the flower-shaped titanium dioxide and the N-doped graphene quantum dots in ultrapure water, and placing the ultra-pure water into a high-pressure kettle for hydrothermal reaction to obtain the titanium dioxide/graphene quantum dot composite material. The result of the photocatalytic performance test shows that the quantum dot composite material has higher photocatalytic activity and obviously improves the degradation capability of organic pollutants.
Description
Technical Field
The invention relates to a preparation method of a titanium dioxide composite material, in particular to a preparation method of a functionalized graphene quantum dot/titanium dioxide composite material, which is mainly used as a photocatalyst for degrading organic pollutants in wastewater, and belongs to the field of material preparation and the field of photocatalytic application.
Background
Water is one of ten major problems together with human, energy, food safety, environmental pollution, and the like. Especially in developing countries, diseases and the like spread rapidly due to the inability to implement an effective and extensive infrastructure for purifying water and disinfecting. In this sense, the application of photocatalysis to the purification of water and wastewater can provide great application prospects for solving the urgent water environment problem. Such as photodegradation or conversion of organic pollutants, removal of toxicity of heavy metal ions, etc. Titanium dioxide (TiO)2) The basic photocatalysis is easy to industrialize, good in stability, rich in reserves, non-toxic and high in photoactivityHas attracted great attention. Graphene quantum dots as a novel zero-dimensional carbon nanomaterial are different from micron-sized zero-band-gap graphene materials, the size of the graphene quantum dots is usually below 10 nanometers, and an energy band of an exciton is opened to form a semiconductor material with adjustable bandwidth due to quantum confinement effect of exciton confinement, so that the graphene quantum dots are widely applied to fluorescence imaging, electrochemical sensing, drug delivery, dye batteries, photocatalysis and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a functionalized graphene quantum dot/titanium dioxide composite material; the invention simultaneously researches the photocatalytic performance of the prepared functionalized graphene quantum dot/titanium dioxide composite material.
Preparation of functionalized graphene quantum dot/titanium dioxide composite material
(1) Preparation of flower-like titanium dioxide
Dispersing titanium (IV) tetraisopropoxide in ethylene glycol under an acidic environment by taking polyvinylpyrrolidone (PVP) as a dispersing agent, and fully stirring to obtain a titanium solution; placing the titanium solution in a stainless steel autoclave, and reacting for 12-13 h at 160-165 ℃; cooling to room temperature, filtering the reaction solution, washing the product with distilled water and ethanol for several times, and drying at 60-65 ℃ for 12-12.5 h to obtain yellow powdery titanium dioxide; and then placing the yellow powdery titanium dioxide in a vacuum tube furnace, and annealing for 1.5-2 h at 550-600 ℃ in an air atmosphere to obtain white flower-shaped titanium dioxide marked as FT.
Adding a dispersing agent polyvinylpyrrolidone in a form of aqueous solution with the concentration of 5-6 mg/mL; the volume ratio of the polyvinylpyrrolidone aqueous solution to the titanium tetraisopropoxide is 1: 30-1: 35.
(2) Preparation of N-doped graphene quantum dots
Mixing citric acid and urea according to the mass ratio of 1: 1-1: 1.2, grinding for 20-25 min, heating to 175-180 ℃, melting the mixed powder, and slowly changing the white color into a yellow solution; and after the solution is cooled to room temperature, adding ultrapure water, performing ultrasonic treatment for 1.5-2 h, centrifuging, collecting supernatant, dialyzing the supernatant for 40-48 h by using a dialysis bag, and performing dialysis and freeze drying to obtain brown powdery N-doped graphene quantum dots which are marked as N-GQDs.
The centrifugal speed is 12000-13000 rpm;
the dialysis bag is 3000-8000 Da;
(3) preparation of titanium dioxide/graphene quantum dot composite material
Ultrasonically dispersing white flower-shaped titanium dioxide (FT) and N-doped graphene quantum dots (N-GQDs) in ultrapure water according to the mass ratio of 1: 5-1: 50, then placing the materials in an autoclave, keeping the temperature at 119-120 ℃ for 5.5-6 h, cooling to room temperature, filtering, washing with the ultrapure water and ethanol for several times, and drying to obtain the titanium dioxide/graphene quantum dot composite material marked as FT/N-GQDs.
Structure and performance of titanium dioxide/graphene quantum dot composite material
FIG. 1 is an X-ray diffraction (XRD) pattern of NGQDs, FT, FT-NGQDs prepared by the present invention. The FT-NGQDs plots of 2 θ = 27.4 °, 36.1 °, 41.2 °, 54.3 °, 56.7 °, and 69.0 ° correspond to (110), (101), (111), (211), (220), (301), indicating that we have produced rutile phase TiO2. The diffraction peak at 2 theta = 26.2 ° is the characteristic diffraction peak of the (002) crystal plane of graphite, and the diffraction peak of NGQDs at 2 theta = 11.3 ° indicates that the NGQDs prepared by us have many oxygen-containing groups.
Fig. 2 is a raman spectrum of the titanium dioxide/graphene quantum dot composite material prepared by the present invention. FT and FT-NGQDs in the figure have rutile phase TiO2Characteristic peak of 138cm-1，226 cm-1，441 cm-1，606 cm-1The Raman spectrum of FT-NGQDs has the characteristic D (1350 cm) of graphene-1) Band sum G (1599 cm)-1) Bands, indicating that NGQDs are present on the surface of FT-NGQDs samples.
Fig. 3 is an ultraviolet spectrum of the titanium dioxide/graphene quantum dot composite material prepared by the invention. As can be seen from FIG. 3, the absorbance of the titanium dioxide/graphene quantum dot composite material is obviously enhanced at the visible light region (400-800 nm) compared with that of pure titanium dioxide, which indicates that the absorption capacity of the composite material to visible light is obviously improved, and therefore, the releasable photocatalytic activity of the composite material is obviously improved compared with that of pure titanium dioxide.
Fig. 4 is a photocatalytic degradation diagram of the titanium dioxide/graphene quantum dot composite material prepared by the present invention. As can be seen from FIG. 4, the performance of the titanium dioxide/graphene quantum dot composite material is greatly improved compared with that of pure titanium dioxide in the aspect of photocatalytic degradation of rhodamine B. The ordinate in the figure represents the percentage value of the degradation concentration in the original total concentration, and the larger the linear slope of the graph is, the higher the photocatalytic activity is, the stronger the pollutant degradation capability is.
In summary, the present invention has the following advantages over the prior art:
1. according to the invention, flower-shaped titanium dioxide and graphene quantum dots are compounded in a high-pressure reaction kettle to obtain titanium dioxide successfully loaded with the graphene quantum dots, so that the composite material has higher photocatalytic activity, and can be used for preparing photolysis water, energy storage materials, environment protection materials and the like, thereby the application of the titanium dioxide composite material is wider;
2. when nitrogen is introduced into a carbon skeleton of the graphene quantum dot, the electronic characteristic of the quantum dot can be adjusted, active sites are formed on the surface of the graphene quantum dot, and more excellent electrical performance and optical performance are obtained; the photocatalytic activity of titanium dioxide can be effectively improved by compounding the N-doped graphene quantum dots, the time for degrading organic pollutants is greatly shortened, and the degradation can be completed in 60 min.
Drawings
Fig. 1 is an XRD of the functionalized graphene quantum dot/titanium dioxide composite material prepared by the present invention.
Fig. 2 is a raman spectrum of the titanium dioxide/graphene quantum dot composite material prepared by the present invention.
Fig. 3 is an ultraviolet spectrum of the titanium dioxide/graphene quantum dot composite material prepared by the invention.
Fig. 4 is a photocatalytic diagram of the functionalized graphene quantum dot/titanium dioxide composite material prepared by the method.
Detailed Description
The preparation, performance and the like of the polyphenylene sulfide/graphene quantum dot composite material prepared by the invention are further explained by specific examples.
Example 1
(1) Preparing flower-shaped titanium dioxide: 0.5mL of titanium (IV) isopropoxide was slowly added dropwise to 6mL of concentrated HCl and stirred at room temperature for 1 h. Then 15mL of PVP (6 mg/mL) aqueous solution was added slowly with stirring, and after stirring for 2 hours, 45mL of ethylene glycol was mixed with the above solution and stirred for 2 hours. The mixture was placed in a 100mL stainless steel autoclave lined with Teflon and held at 160 ℃ for 12h in a forced air oven and cooled to room temperature. Filtering the reacted solution, washing the solution for a plurality of times by using distilled water and ethanol, and drying the solution for 12 hours at the temperature of 60 ℃; putting the obtained yellow powder into a porcelain boat, putting the porcelain boat into a vacuum tube furnace, and then annealing the porcelain boat for 2 hours at 550 ℃ in the air atmosphere to remove PVP residues, wherein the product is flower-shaped TiO2（FT）；
(2) Preparing N-doped graphene quantum dots: mixing 2.1g of citric acid and 2.4g of urea, grinding for 20min, adding the ground powder into a round-bottom flask, heating at 180 ℃, melting the powder in the heating process, slowly changing the powder from white to yellow solution, cooling the obtained solution to room temperature after 30 min, adding 50mL of ultrapure water, carrying out ultrasonic treatment for 2h, centrifuging at 13000rpm for 20min, collecting supernatant, dialyzing for 48h by using a dialysis bag (3000 Da), and finally freeze-drying the dialyzate to obtain N-GQDs brown powder;
(3) preparing titanium dioxide/graphene quantum dots: 0.1g of FT and 0.5mg of NGQDs were ultrasonically dispersed in 50mL of ultrapure water for 30 minutes, and the mixture was placed in a 100mL Teflon-lined stainless steel autoclave, maintained at 120 ℃ for 6 hours, cooled to room temperature, filtered, washed with ultrapure water and ethanol several times, and dried at 60 ℃ overnight to give FT/N-GQDs. The sample was labeled FT-NGQDs-0.5.
The degradation performance of the composite material on organic pollutants is improved compared with that of pure titanium dioxide, as can be seen from figure 4, the degradation rate of the pure titanium dioxide is 60%, the degradation performance of the composite material is improved by about 25% -40% compared with that of the pure material, and the organic pollutants can be completely degraded by the doping amount in one hour degradation time.
Example 2
(1) Preparing flower-shaped titanium dioxide: the same as example 1;
(2) preparing N-doped graphene quantum dots: the same as example 1;
(3) preparing titanium dioxide/graphene quantum dots: 0.1g of FT and 1mg of NGQDs were ultrasonically dispersed in 50mL of ultrapure water for 30 minutes, and the mixture was placed in a 100mL Teflon-lined stainless steel autoclave, which was then kept at 120 ℃ for 6 hours, cooled to room temperature, filtered, washed several times with ultrapure water and ethanol, and dried at 60 ℃ overnight to give FT/N-GQDs. The sample was labeled FT-NGQDs-1.
Compared with FT-NGQDs-0.5, the degradation performance of the composite material to organic pollutants is improved by about 5 percent.
Example 3
(1) Preparing flower-shaped titanium dioxide: the same as example 1;
(2) preparing N-doped graphene quantum dots: the same as example 1;
(3) preparing titanium dioxide/graphene quantum dots: 0.1g of FT and 3mg of NGQDs were ultrasonically dispersed in 50mL of ultrapure water for 30 minutes, and the mixture was placed in a 100mL Teflon-lined stainless steel autoclave, which was then kept at 120 ℃ for 6 hours, cooled to room temperature, filtered, washed several times with ultrapure water and ethanol, and dried at 60 ℃ overnight to give FT/N-GQDs. The sample was labeled FT-NGQDs-3.
Compared with FT-NGQDs-1, the composite material has improved degradation performance on organic pollutants by 10 percent.
Example 4
(1) Preparing flower-shaped titanium dioxide: the same as example 1;
(2) preparing N-doped graphene quantum dots: the same as example 1;
(3) preparing titanium dioxide/graphene quantum dots: 0.1g of FT and 5mg of NGQDs were ultrasonically dispersed in 50mL of ultrapure water for 30 minutes, and the mixture was placed in a 100mL Teflon-polytetrafluoroethylene-lined stainless steel autoclave, maintained at 120 ℃ for 6 hours, cooled to room temperature, filtered, washed several times with ultrapure water and ethanol, and dried at 60 ℃ overnight to give FT/N-GQDs. Sample markers FT-NGQDs-5
Compared with FT-NGQDs-3, the degradation performance of the composite material to organic pollutants is reduced by about 10 percent; but compared with pure titanium dioxide, the degradation performance of the composite material on organic pollutants is improved by about 30 percent.
Claims (5)
1. A preparation method of a functionalized graphene quantum dot/titanium dioxide composite material comprises the following process steps:
(1) preparing flower-shaped titanium dioxide: dispersing titanium (IV) tetraisopropoxide in ethylene glycol under an acidic environment by taking polyvinylpyrrolidone as a dispersing agent, and fully stirring to obtain a titanium solution; placing the titanium solution in a stainless steel autoclave, and reacting for 12-13 h at 160-165 ℃; cooling to room temperature, filtering, washing the product with distilled water and ethanol for several times, and drying at 60-65 ℃ for 12-12.5 h to obtain yellow powdery titanium dioxide; then placing the yellow powdery titanium dioxide in a vacuum tube furnace, and annealing for 1.5-2 hours at 550-600 ℃ in an air atmosphere to obtain white flower-shaped titanium dioxide; adding a dispersant polyvinylpyrrolidone into an aqueous solution with the concentration of 5-6 mg/mL; the volume ratio of the polyvinylpyrrolidone aqueous solution to the titanium tetraisopropoxide is 1: 30-1: 35;
(2) preparing N-doped graphene quantum dots: mixing and grinding citric acid and urea for 20-25 min, heating to 175-180 ℃, melting the mixed powder, and slowly changing the white color into a yellow solution; adding ultrapure water into the solution after the solution is cooled to room temperature, ultrasonically treating the solution for 1.5-2 hours, centrifuging the solution, collecting supernatant, dialyzing the supernatant for 40-48 hours by using a dialysis bag, and freeze-drying the dialyzed solution to obtain brown powdery N-doped graphene quantum dots which are marked as N-GQDs;
(3) preparing a titanium dioxide/graphene quantum dot composite material: ultrasonically dispersing white flower-shaped titanium dioxide and N-doped graphene quantum dots in ultrapure water, then placing the mixture in a high-pressure kettle, keeping the temperature at 115-120 ℃ for 5.5-6 h, cooling to room temperature, filtering, washing with ultrapure water and ethanol for several times, and drying to obtain the titanium dioxide/graphene quantum dot composite material which is marked as FT/N-GQDs.
2. The preparation method of the functionalized graphene quantum dot/titanium dioxide composite material according to claim 1, wherein the preparation method comprises the following steps: in the step (2), the mass ratio of the citric acid to the urea is 1: 1-1: 1.2.
3. The preparation method of the functionalized graphene quantum dot/titanium dioxide composite material according to claim 1, wherein the preparation method comprises the following steps: in the step (2), the centrifugal speed is 12000-13000 rpm.
4. The preparation method of the functionalized graphene quantum dot/titanium dioxide composite material according to claim 1, wherein the preparation method comprises the following steps: in the step (2), the dialysis bag is 3000-8000 Da.
5. The preparation method of the functionalized graphene quantum dot/titanium dioxide composite material according to claim 1, wherein the preparation method comprises the following steps: in the step (3), the mass ratio of the white flower-shaped titanium dioxide to the N-doped graphene quantum dots is 1: 5-1: 50.
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| CN110624532B (en) * | 2019-09-19 | 2021-08-10 | 华南理工大学 | TiO 22-BiVO4-graphene ternary composite photocatalytic material and preparation method thereof |
| CN110801857A (en) * | 2019-12-02 | 2020-02-18 | 山东建筑大学 | Method for preparing titanium dioxide-nitrogen doped graphene composite photocatalytic material |
| CN111097481A (en) * | 2019-12-30 | 2020-05-05 | 山东泰和水处理科技股份有限公司 | Preparation method of titanium and nitrogen-containing doped graphene quantum dot molecular sieve |
| CN111945138B (en) * | 2020-08-17 | 2023-05-26 | 南京信息工程大学 | Graphene quantum dot-based functionalized titanium dioxide/chlorella nanocomposite as well as preparation method and application thereof |
| CN113117661A (en) * | 2021-03-09 | 2021-07-16 | 广西师范大学 | Catalyst of graphene quantum dot doped titanium dioxide, preparation method and application thereof |
| CN114031112B (en) * | 2021-09-15 | 2023-06-16 | 中国科学技术大学 | Titanium oxide photo-thermal material, preparation method thereof and application thereof in photo-thermal tumor treatment under second biological infrared window |
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| CN104815637A (en) * | 2015-04-02 | 2015-08-05 | 西北师范大学 | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material |
| CN105289689A (en) * | 2015-11-07 | 2016-02-03 | 南昌航空大学 | Synthesis and application of nitrogen-doped graphene quantum dot/similar-graphene phase carbon nitride composite material |
| CN109046304A (en) * | 2018-09-04 | 2018-12-21 | 西北师范大学 | Hydrogenate the preparation method of the flower-shaped titanium dioxide of grey |
| CN109395709A (en) * | 2018-07-12 | 2019-03-01 | 重庆交通大学 | A kind of graphene quantum dot/two dimension titanium dioxide and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815637A (en) * | 2015-04-02 | 2015-08-05 | 西北师范大学 | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material |
| CN105289689A (en) * | 2015-11-07 | 2016-02-03 | 南昌航空大学 | Synthesis and application of nitrogen-doped graphene quantum dot/similar-graphene phase carbon nitride composite material |
| CN109395709A (en) * | 2018-07-12 | 2019-03-01 | 重庆交通大学 | A kind of graphene quantum dot/two dimension titanium dioxide and preparation method thereof |
| CN109046304A (en) * | 2018-09-04 | 2018-12-21 | 西北师范大学 | Hydrogenate the preparation method of the flower-shaped titanium dioxide of grey |
Non-Patent Citations (1)
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| Ultrathin sub-3 nm nitrogen-doped graphene quantum dot layers coated TiO2 nanocomposites as high-performance photocatalysts;Sejung Kim et al.;《Chemical Physics Letters》;20181024;第714卷;第1-5页 * |
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