CN110801857A - Method for preparing titanium dioxide-nitrogen doped graphene composite photocatalytic material - Google Patents
Method for preparing titanium dioxide-nitrogen doped graphene composite photocatalytic material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 80
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 53
- IWLUJCZGMDWKRT-UHFFFAOYSA-N azane oxygen(2-) titanium(4+) Chemical compound N.[O-2].[Ti+4].[O-2] IWLUJCZGMDWKRT-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 19
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 19
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 14
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 8
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- 238000000870 ultraviolet spectroscopy Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 7
- 229940012189 methyl orange Drugs 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 239000012476 oxidizable substance Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 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
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B01J35/51—
Abstract
The invention relates to a method for preparing a titanium dioxide-nitrogen doped graphene composite photocatalytic material, which comprises the steps of adding titanium sulfate into a hydrofluoric acid aqueous solution, carrying out ultrasonic treatment, uniformly stirring, transferring into a polytetrafluoroethylene reaction kettle, reacting at 180 ℃ for 12 hours, washing, drying to obtain titanium dioxide powder with a partial hollow microspherical structure, mixing with nitrogen doped graphene in deionized water, carrying out ultrasonic treatment for 3 hours, transferring into the polytetrafluoroethylene reaction kettle, reacting at 180 ℃ for 12 hours, naturally cooling, centrifuging, and drying to obtain the titanium dioxide-nitrogen doped graphene composite photocatalytic material. The preparation process is simple and convenient, the reaction cost is low, other additives or catalysts are not needed in the reaction process, the obtained composite photocatalytic material has excellent photocatalytic activity, the utilization rate of sunlight is high, and the treatment cost of dye wastewater is effectively reduced.
Description
Technical Field
The invention belongs to the technical field of inorganic composite materials, and particularly relates to the field of preparation of a titanium dioxide-nitrogen doped graphene composite photocatalytic material.
Background
The titanium dioxide has the advantages of good light corrosion resistance and catalytic activity, high chemical stability, low price, no toxicity, no harm, recyclability and the like, and is the best photocatalyst recognized at present. But TiO 22The forbidden band width of the light-emitting diode is large, the utilization rate of sunlight is low, the coincidence rate of photo-generated electron-hole pairs is high, and the light quantum efficiency is low. In addition, TiO2Easy agglomeration, reduced specific surface area, influence on the adsorption capacity of the dye, and low photocatalytic efficiency.
Graphene is a novel two-dimensional carbon nanomaterial, has good mechanical, electrical and optical properties, has important application prospects in the fields of materials, energy, medicine, environment and the like, and is a novel material with future revolutionary property. The graphene has a large specific surface area and high conductivity, and an interaction effect exists between the graphene and titanium dioxide crystal grains, so that the graphene can remarkably improve the adsorption property and photocatalytic activity of the titanium dioxide. Doping graphene is one of important ways for realizing graphene functionalization, and the physicochemical properties of graphene can be effectively regulated and controlled. The graphene is doped with nitrogen, so that the conductivity type can be adjusted, the free carrier density is improved, the active sites adsorbed on the surface of the graphene are increased, and the like. Therefore, nitrogen-doped graphene shows more excellent properties than pure graphene.
Patent CN 109364992A discloses a nitrogen-doped graphene/nano titanium dioxide photocatalyst and a preparation method and application thereof, but the prepared material is low in adsorption rate and degradation rate, and the recycling degree of the material is not high, so that the research on a titanium dioxide-nitrogen-doped graphene composite photocatalytic material which is high in adsorption rate and degradation rate and can be recycled is significant.
Disclosure of Invention
Aiming at the problems of low adsorption performance, low catalytic efficiency and low cyclability of the composite photocatalytic material in the prior art, the invention provides a preparation method of the titanium dioxide-nitrogen doped graphene composite photocatalytic material, and the prepared composite photocatalytic material has high adsorption rate and degradation rate and can be recycled.
The invention is realized by the following technical scheme:
a method for preparing a titanium dioxide-nitrogen doped graphene composite photocatalytic material comprises the following steps:
(1) adding titanium sulfate into a hydrofluoric acid aqueous solution, carrying out ultrasonic treatment for 15 minutes, stirring for 10-20 minutes, transferring into a polytetrafluoroethylene reaction kettle, reacting for 12 hours at 180 ℃, washing, and drying to obtain hollow titanium dioxide powder;
the titanium dioxide powder is of a partially hollow microspherical structure;
(2) mixing the titanium dioxide powder prepared in the step (1) and nitrogen-doped graphene in deionized water, carrying out ultrasonic treatment for 3 hours, transferring the mixture into a polytetrafluoroethylene reaction kettle, reacting for 12 hours at 180 ℃, naturally cooling, centrifuging, and drying to obtain the titanium dioxide-nitrogen-doped graphene composite photocatalytic material.
Preferably, the concentration of the hydrofluoric acid aqueous solution in the step (1) is 160 mmol/L.
Preferably, the addition amount of the titanium sulfate in the step (1) is 2.4g of titanium sulfate per liter of hydrofluoric acid aqueous solution.
Preferably, the nitrogen-doped graphene in the step (1) is prepared by the following method: adding the graphene oxide dispersion into a beaker, and adding the graphene oxide dispersion and graphene oxide in a mass ratio of 1: 5, stirring and reacting for 30 minutes, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 3 hours at 160 ℃, naturally cooling, centrifuging, and freeze-drying to obtain the nitrogen-doped graphene.
Preferably, the graphene oxide is prepared by adopting an improved Hummers method.
Preferably, the adding amount of the nitrogen-doped graphene in the step (2) is 1-9% of the mass of titanium dioxide; preferably, the adding amount of the nitrogen-doped graphene is 5-7% of the mass of the titanium dioxide.
Preferably, the drying condition is 60 ℃ for 12 hours.
Titanium dioxide is a commonly used photocatalyst, which is excited by light to generate photo-generated electron-hole pairs, and the process is that electrons excited by light are transferred from a valence band to a conduction band, so that photo-generated electrons are formed in the conduction band, and photo-generated holes are formed in the valence band. When reaching the surface of the titanium dioxide, the photoproduced electrons are captured by the oxidizable substances to oxidize the electron acceptor, and the holes receive electrons of the donor to oxidize the donor, so that the methyl orange can be degraded by utilizing the redox characteristic of a photoproduced electron-hole pair. The N atoms have atomic radii similar to those of the C atoms, so that the N atoms can be used as electron donors to dope the graphene in a substitution mode, and the generated N-doped graphene has a plurality of excellent performances, such as opening an energy band gap, adjusting the conductivity type, changing the electronic structure of the graphene, and improving the free carrier density of the graphene, so that the conductivity and stability of the graphene are improved, the active sites of metal particles adsorbed on the surface of the graphene are increased, and the like. The titanium dioxide-nitrogen doped graphene composite photocatalytic material can degrade complex organic matters into CO under the irradiation of ultraviolet light and visible light2And H2And inorganic substances such as O and the like eliminate the harm of the organic substances to the environment and human beings.
In order to research the photocatalytic degradation performance of the composite material, catalytic reactions were performed under ultraviolet light and sunlight respectively, an ultraviolet light source was a 250w high-pressure mercury lamp (365 nm), the distance from the vessel was 15cm, samples were taken every 10min, after centrifugation, the supernatant was taken, the absorbance was measured with an ultraviolet-visible spectrophotometer, and the photocatalytic efficiency was calculated according to the formula. The visible light catalysis test selects an outdoor place on a sunny day for 5 hours, samples are taken every 30min, and the method for calculating the photocatalysis efficiency is the same as the method.
The adsorption capacity of the composite material to methyl orange is calculated according to the following formula:
in the formula: cd0Is the initial concentration of the methyl orange solution; cdtThe concentration of the methyl orange solution at the reaction time t is shown.
The degradation efficiency of the composite material on methyl orange is calculated according to the following formula:
in the formula Cd0Is the initial concentration of methyl orange, CdtThe concentration of methyl orange at the reaction time t is shown.
Advantageous effects
(1) The composite material prepared by the invention adopts a hydrothermal synthesis method, and has the advantages of simple and convenient reaction process, low reaction cost, simple reaction conditions and the like, no other additive or catalyst is needed in the reaction process, the titanium dioxide-nitrogen doped graphene composite photocatalytic material obtained by the reaction has excellent photocatalytic activity, the utilization rate of sunlight is high, and the treatment cost of dye wastewater is effectively reduced.
(2) The reaction system of the invention uses HF concentration of 160mmol/L, partial hollow microspherical titanium dioxide powder is obtained under the concentration and the preparation method, and the adsorption efficiency and the degradation efficiency are obviously improved after the titanium dioxide powder is doped with nitrogen-doped graphene.
(3) The titanium dioxide-nitrogen doped graphene composite photocatalytic material prepared by the invention is easy to recycle, and the recycled material still maintains high catalytic degradation property, thereby being beneficial to recycling of the material.
Drawings
FIG. 1 shows TiO prepared in example step (1)2Powder electron microscope images;
FIG. 2 is an electron microscope image of the titanium dioxide-nitrogen doped graphene composite photocatalytic material prepared in example 1;
FIG. 3 shows TiO prepared in example 12An X-ray diffraction pattern of the composite photocatalytic material;
FIG. 4 is a graph showing the change of the adsorption amount of the composite photocatalytic material prepared in examples 1 to 5 with respect to the reaction time;
FIG. 5 is a graph showing the degradation rate of the composite photocatalytic material prepared in examples 1 to 5 under ultraviolet light as a function of degradation time;
FIG. 6 is a change curve of the degradation rate of the composite photocatalytic material prepared in examples 1-5 under sunlight with degradation time;
FIG. 7 shows the degradation rate of the composite photocatalytic material prepared in example 1 under sunlight as a function of the cycle number;
FIG. 8 is a graph showing the effect of the composite photocatalytic material on the degradation rate at different concentrations of HF in example 1 and comparative example 1;
FIG. 9 is a graph showing the degradation rate of the composite photocatalytic materials prepared in example 1 and comparative example 1 under ultraviolet light as a function of degradation time;
FIG. 10 is a graph showing the degradation rate of the composite photocatalytic materials prepared in example 1 and comparative example 1 under sunlight as a function of degradation time.
Detailed Description
In order to make the technical solutions of the present invention better understood, the following description is provided clearly and completely, and other similar embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present application based on the embodiments in the present application.
Example 1
(1) 30mL of HF (160 mmol/L) was added dropwise to 50mL of H2O, and 192mg of Ti (SO) was added4)2Stirring for 15 minutes on a magnetic stirrer after ultrasonic treatment for 15 minutes, transferring the solution into a reaction kettle with a 100mL polytetrafluoroethylene lining, keeping the reaction kettle at 180 ℃ for 12 hours, centrifuging the obtained product after the reaction is finished, washing the product for many times by using absolute ethyl alcohol and deionized water to remove impurities, drying the sample in a vacuum oven at 60 ℃ for 12 hours, and obtaining white powder, namely nano TiO2The electron microscope image is shown in fig. 1, and the powder is known to be a partially hollow microspherical structure through the electron microscope image;
(2) preparing Graphene Oxide (GO) by adopting an improved Hummers method, adding 30mL of GO into a beaker after the GO is prepared, and then adding the mixture of GO and urea in a mass ratio of 1: 5, adding urea, stirring for 30 minutes, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 3 hours at 160 ℃, naturally cooling, centrifuging for several times, and freeze-drying to obtain nitrogen-doped (NG) graphene;
(3) 60 mg of TiO2Powder, 3.0mg NG (added amount of NG is TiO)27 wt%) and 50mL of deionized water are added into a test tube, after ultrasonic treatment is carried out for 3 hours, the mixed solution is poured into a 100mL reaction kettle with a polytetrafluoroethylene lining, the reaction kettle reacts for 12 hours at 180 ℃, the centrifugation is carried out, absolute ethyl alcohol and the deionized water are used for washing for multiple times to remove impurities, a sample is dried for 12 hours in a vacuum oven at 60 ℃, and the obtained product is the titanium dioxide-nitrogen doped graphene composite photocatalytic material, the electron microscope picture of which is shown in figure 2, and as can be seen from figure 2, the structure of the titanium dioxide and the nitrogen doped graphene after being compounded is still in a partially hollow microspherical structure and is tightly connected with the nitrogen doped graphene; FIG. 3 is TiO2And the X-ray diffraction pattern of the titanium dioxide-nitrogen doped graphene composite photocatalytic material shows that TiO is2The titanium dioxide-nitrogen doped graphene composite photocatalytic material and the composite material are anatase crystals, and the diffraction peak of the titanium dioxide-nitrogen doped graphene composite photocatalytic material is obviously weaker than that of TiO2This is due to NG and TiO2Due to the interaction between them.
Example 2
The steps (1) and (2) are the same as the steps (1) and (2) in example 1;
60 mg of TiO2Powder, 0.6mg NG (added TiO)21 wt%) and 50mL of deionized water are added into a test tube, after ultrasonic treatment is carried out for 3 hours, the mixed solution is poured into a reaction kettle with a 100mL polytetrafluoroethylene lining, the reaction kettle is reacted for 12 hours at 180 ℃, centrifugation is carried out, absolute ethyl alcohol and deionized water are used for washing for multiple times to remove impurities, a sample is dried for 12 hours in a vacuum oven at 60 ℃, and the obtained product is the titanium dioxide-nitrogen doped graphene composite photocatalytic material, the structure of the titanium dioxide and the nitrogen doped graphene is still in a partially hollow microspherical structure after the titanium dioxide is compounded with the nitrogen doped graphene, and the titanium dioxide-nitrogen doped graphene composite photocatalytic material is tightly connected with the nitrogen doped graphene.
Example 3
The steps (1) and (2) are the same as the steps (1) and (2) in example 1;
will be 60mg TiO2Powder, 1.8 mg of NG (the amount of NG added is TiO)23 wt%) and 50mL of deionized water are added into a test tube, after ultrasonic treatment is carried out for 3 hours, the mixed solution is poured into a 100mL reaction kettle with a polytetrafluoroethylene lining, the reaction kettle is reacted for 12 hours at 180 ℃, centrifugation is carried out, absolute ethyl alcohol and deionized water are used for washing for multiple times to remove impurities, a sample is dried for 12 hours in a vacuum oven at 60 ℃, the obtained product is the titanium dioxide-nitrogen doped graphene composite photocatalytic material, and the structure of the titanium dioxide and the nitrogen doped graphene is still in a partially hollow microspherical structure after the titanium dioxide and the nitrogen doped graphene are compounded, and the titanium dioxide and the nitrogen doped graphene are tightly connected.
Example 4
The steps (1) and (2) are the same as the steps (1) and (2) in example 1;
60 mg of TiO2Powder, 4.2 mg NG (added TiO)25 wt%) and 50mL of deionized water are added into a test tube, after ultrasonic treatment is carried out for 3 hours, the mixed solution is poured into a 100mL reaction kettle with a polytetrafluoroethylene lining, the reaction kettle reacts for 12 hours at 180 ℃, the centrifugation is carried out, absolute ethyl alcohol and the deionized water are used for washing for multiple times to remove impurities, a sample is dried for 12 hours in a vacuum oven at 60 ℃, the obtained product is the titanium dioxide-nitrogen doped graphene composite photocatalytic material, and the structure of the titanium dioxide and the nitrogen doped graphene is still in a partially hollow microspherical structure and is tightly connected with the nitrogen doped graphene.
Example 5
The steps (1) and (2) are the same as the steps (1) and (2) in example 1;
60 mg of TiO2Powder, 5.4mg NG (added TiO)29 wt%) and 50mL of deionized water are added into a test tube, after ultrasonic treatment is carried out for 3 hours, the mixed solution is poured into a reaction kettle with a 100mL polytetrafluoroethylene lining, the reaction kettle reacts for 12 hours at 180 ℃, the centrifugation is carried out, absolute ethyl alcohol and deionized water are used for washing for multiple times to remove impurities, a sample is dried for 12 hours in a vacuum oven at 60 ℃, the obtained product is the titanium dioxide-nitrogen doped graphene composite photocatalytic material, and the titanium dioxide and the nitrogen doped graphene composite photocatalyst have the structure after being compoundedStill has a partially hollow microspherical structure and is tightly connected with the nitrogen-doped graphene.
Comparative example 1
(1) 30mL of HF (the concentrations of HF are 0mmol/L (water), 40 mmol/L, 80 mmol/L, 120mmol/L and 160mmol/L, respectively) were added dropwise to 50mL of H2O, and 192mg of Ti (SO) was added4)2Stirring for 15 minutes on a magnetic stirrer after ultrasonic treatment for 15 minutes, transferring the solution into a reaction kettle with a 100mL polytetrafluoroethylene lining, keeping the reaction kettle at 180 ℃ for 12 hours, centrifuging the obtained product after the reaction is finished, washing the product for many times by using absolute ethyl alcohol and deionized water to remove impurities, drying the sample in a vacuum oven at 60 ℃ for 12 hours, and obtaining white powder, namely nano TiO2The powder is shown in figure 1, and is known to be a partially hollow microspherical structure through an electron microscope picture;
(2) preparing Graphene Oxide (GO) by adopting an improved Hummers method, adding 30mL of GO into a beaker after the GO is prepared, and then adding the mixture of GO and urea in a mass ratio of 1: 5, adding urea, stirring for 30 minutes, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 3 hours at 160 ℃, naturally cooling, centrifuging for a plurality of times, and freeze-drying to obtain nitrogen doping (NG);
(3) 60 mg of the TiO prepared in step (1) were each separately added2Powder, 3.0mg NG (added amount of NG is TiO)25 wt%) and 50mL of deionized water are added into a test tube, after ultrasonic treatment is carried out for 3 hours, the mixed solution is poured into a 100mL reaction kettle with a polytetrafluoroethylene lining, the reaction kettle is reacted for 12 hours at 180 ℃, centrifugation is carried out, absolute ethyl alcohol and deionized water are used for washing for multiple times to remove impurities, a sample is dried for 12 hours in a vacuum oven at 60 ℃, and the obtained product is the titanium dioxide-nitrogen doped graphene composite photocatalytic material.
Comparative example 2
(1) 30mL of HF (160 mmol/L) was added dropwise to 50mL of H2O, and 192mg of Ti (SO) was added4)2After 15 minutes of sonication, the solution was stirred on a magnetic stirrer for 15 minutes, then transferred to a 100mL Teflon lined reactor andkeeping the reaction solution at 180 ℃ for 12 hours, centrifuging the obtained product after the reaction is finished, washing the product by absolute ethyl alcohol and deionized water for many times to remove impurities, and drying the sample in a vacuum oven at 60 ℃ for 12 hours to obtain white powder, namely nano TiO2The powder is shown in figure 1, and is known to be a partially hollow microspherical structure through an electron microscope picture;
(2) 60 mg of TiO2Powder, 3.0mg graphene (added amount of graphene is TiO)25 wt%) and 50mL of deionized water are added into a test tube, after ultrasonic treatment is carried out for 3 hours, the mixed solution is poured into a 100mL reaction kettle with a polytetrafluoroethylene lining, the reaction kettle reacts for 12 hours at 180 ℃, the centrifugation is carried out, absolute ethyl alcohol and deionized water are used for washing for multiple times to remove impurities, a sample is dried for 12 hours in a vacuum oven at 60 ℃, and the obtained product is the titanium dioxide-graphene composite photocatalytic material.
Analysis of adsorption performance and photocatalytic performance:
1. 0.1g of the composite materials of examples 1-5 with different NG doping concentrations were respectively put into 100ml of methyl orange solution (pH = 3) with a concentration of 20mg/l, stirred for 1 hour under dark conditions, sampled every 10 minutes, reacted for 60min, the sample was centrifuged, the supernatant was taken, absorbance was measured at 464nm by an ultraviolet-visible spectrophotometer, and the adsorption value of the composite materials to the methyl orange dye was calculated, and the results are shown in FIG. 4.
2. 0.1g of each of the composite materials of examples 1 to 5 with different NG doping concentrations was put into 100ml of a methyl orange solution (pH = 3) with a concentration of 20mg/l, stirred for 1 hour under a dark condition, and subjected to photocatalytic degradation under an ultraviolet light (365 nm) condition. The ultraviolet light source is a 250w high-pressure mercury lamp, the distance from the container is 15cm, samples are taken every 10min, and the reaction time is 60 min. Centrifuging a sample, taking supernatant, measuring absorbance by using an ultraviolet-visible spectrophotometer, and calculating the photocatalytic efficiency, wherein the change curve of the degradation rate of the composite photocatalytic material under ultraviolet light along with degradation time is shown in figure 5;
3. 0.1g of the composite photocatalytic materials with different NG doping concentrations in the embodiments 1-5 are respectively put into 100ml of methyl orange solution (pH = 3) with the concentration of 20mg/l, stirred for 1 hour under the dark condition, and subjected to photocatalytic degradation under the visible light, the sunlight of an outdoor place on a sunny day is selected as a visible light source, samples are taken once every 30min, and the reaction is carried out for 5 hours. And centrifuging the sample, taking the supernatant, measuring the absorbance by using an ultraviolet-visible spectrophotometer, and calculating the photocatalytic efficiency, wherein the change curve of the degradation rate of the composite photocatalytic material under sunlight along with the degradation time is shown in figure 6.
4. 0.1g of the composite photocatalytic material in example 1 was put into 100ml of a methyl orange solution (pH = 3) with a concentration of 20mg/l, stirred for 1 hour under a dark condition, subjected to photocatalytic reaction under an ultraviolet lamp, sampled after the reaction for 60 minutes, centrifuged, and then supernatant was taken, absorbance was measured with an ultraviolet-visible spectrophotometer, and photocatalytic efficiency was calculated, and then the composite material was washed, dried, recovered, and then the photocatalytic test was repeated, and the degradation rate of methyl orange was changed with the cycle number as shown in FIG. 7.
5. 0.1g of the composite photocatalytic material prepared in example 1 and comparative example 1 is respectively put into 100ml of methyl orange solution (pH = 3) with the concentration of 20mg/l, stirring is carried out for 1 hour under the dark condition, photocatalytic degradation is carried out under the visible light, the visible light source selects the sunlight of an outdoor place in a clear sky, sampling is carried out once every 10min, reaction is carried out for 60min, the supernatant is taken after the sample is centrifuged, the absorbance is measured by an ultraviolet-visible spectrophotometer, the photocatalytic efficiency is calculated, and the change curve of the degradation rate of the composite photocatalytic material under the sunlight along with the degradation time is shown in figure 8.
6. 0.1g of the composite photocatalytic material prepared in the example 1 and the comparative example 2 is respectively put into 100ml of methyl orange solution (pH = 3) with the concentration of 20mg/l, the mixture is stirred for 1 hour under the dark condition, photocatalytic degradation is carried out under the visible light, the visible light source selects the sunlight of an outdoor place on a clear day, sampling is carried out once every 10min, reaction is carried out for 60min, the sample is centrifuged, then the supernatant is taken, the absorbance is measured by an ultraviolet-visible spectrophotometer, the photocatalytic efficiency is calculated, the change curve of the degradation rate of the composite photocatalytic material under the ultraviolet light along with the degradation time is shown in figure 9, the introduction of visible NG can obviously reduce the recombination rate of photo-generated electron-hole pairs, and the photocatalytic performance is improved.
7. 0.1g of the composite photocatalytic material prepared in the example 1 and the comparative example 2 is respectively put into 100ml of methyl orange solution (pH = 3) with the concentration of 20mg/l, the mixture is stirred for 1 hour under the dark condition, photocatalytic degradation is carried out under the visible light, the visible light source selects the sunlight of an outdoor place on a clear day, sampling is carried out once every 10 minutes, reaction is carried out for 60 minutes, the sample is centrifuged, then the supernatant is taken, the absorbance is measured by an ultraviolet-visible spectrophotometer, the photocatalytic efficiency is calculated, the change curve of the degradation rate of the composite photocatalytic material under the sunlight along with the degradation time is shown in figure 10, the introduction of visible NG can obviously narrow the forbidden bandwidth, and the utilization rate of the composite material to the sunlight is improved.
Claims (8)
1. A method for preparing a titanium dioxide-nitrogen doped graphene composite photocatalytic material is characterized by comprising the following steps:
(1) adding titanium sulfate into a hydrofluoric acid aqueous solution, carrying out ultrasonic treatment for 15 minutes, stirring for 10-20 minutes, transferring into a polytetrafluoroethylene reaction kettle, reacting for 12 hours at 180 ℃, washing, and drying to obtain hollow titanium dioxide powder;
the titanium dioxide powder is of a partially hollow microspherical structure;
(2) mixing the titanium dioxide powder prepared in the step (1) and nitrogen-doped graphene in deionized water, carrying out ultrasonic treatment for 3 hours, transferring the mixture into a polytetrafluoroethylene reaction kettle, reacting for 12 hours at 180 ℃, naturally cooling, centrifuging, and drying to obtain the titanium dioxide-nitrogen-doped graphene composite photocatalytic material.
2. The method according to claim 1, wherein the concentration of the aqueous hydrofluoric acid solution in the step (1) is 160 mmol/L.
3. The method according to claim 1, wherein the amount of titanium sulfate added in step (1) is 2.4g per liter of the hydrofluoric acid aqueous solution.
4. The preparation method according to claim 1, wherein the nitrogen-doped graphene in the step (1) is prepared by the following method: adding the graphene oxide dispersion into a beaker, and adding the graphene oxide dispersion and graphene oxide in a mass ratio of 1: 5, stirring and reacting for 30 minutes, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 3 hours at 160 ℃, naturally cooling, centrifuging, and freeze-drying to obtain the nitrogen-doped graphene.
5. The preparation method according to claim 4, wherein the graphene oxide is prepared by a modified Hummers method.
6. The preparation method according to claim 1, wherein the amount of the nitrogen-doped graphene added in the step (2) is 1-9% by mass of the titanium dioxide.
7. The preparation method of claim 6, wherein the amount of the nitrogen-doped graphene added is 5-7% of the mass of the titanium dioxide.
8. The method according to claim 1, wherein the drying is carried out at 60 ℃ for 12 hours.
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