CN113941321A - Preparation method of photocatalyst oxidized titanium dioxide - Google Patents
Preparation method of photocatalyst oxidized titanium dioxide Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 270
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 112
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 239000012286 potassium permanganate Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000010453 quartz Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical group [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000000813 microbial effect Effects 0.000 claims description 2
- 238000004177 carbon cycle Methods 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000003780 insertion Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000005264 electron capture Effects 0.000 description 2
- 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 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100021164 Vasodilator-stimulated phosphoprotein Human genes 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 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
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 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 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 108010054220 vasodilator-stimulated phosphoprotein Proteins 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
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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
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- B01J37/12—Oxidising
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Abstract
The invention relates to the technical field of photocatalysts, in particular to a preparation method for oxidizing titanium dioxide by using a photocatalyst; oxidizing titanium dioxide by using an oxidant, and filtering, washing and drying to prepare an oxidized titanium dioxide photocatalyst; or reacting tetrabutyl phthalate with an oxide in a high-pressure kettle, washing and drying, finally heating in a muffle furnace, cooling and grinding to obtain the oxidized titanium dioxide photocatalyst; the oxidized titanium dioxide has excellent thermal stability, long quality guarantee period, simple preparation method and low cost, and has higher photocatalytic activity under ultraviolet light and visible light compared with pure titanium dioxide.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a preparation method for oxidizing titanium dioxide by using a photocatalyst.
Background
The photocatalyst based on titanium dioxide is widely applied to various aspects such as preparation of clean energy, reduction of carbon dioxide, treatment of organic and microbial wastewater and the like.
Researchers have employed many methods to improve the absorption of light by titanium dioxide, thereby increasing its photocatalytic efficiency in the visible. Doping is considered an effective method. The transition metal ion doping can introduce an electron capture center and change the crystallinity of titanium dioxide, thereby generating defects and reducing the probability of electron and hole recombination. For example, Ce doped titanium dioxide can create new electronic states at the top of the valence band of titanium dioxide, facilitating the separation of electrons from holes. [1] Nonmetal doping can extend the light absorption range of titanium dioxide to ultraviolet light, and Asahi et al [2]2001 reports that titanium dioxide is doped with N in the journal of Science, the insertion of N reduces the band gap of titanium dioxide, generates new state density, changes the transition path of electrons, and changes O2P-Ti 3d of titanium dioxide into N2P-Ti 3d, thereby promoting the generation of effective electrons and improving the photoreactivity of titanium dioxide. In 2011, Chen et al [3] reports deeply hydrogenated black titanium dioxide on Science, disordered crystal faces are introduced on a titanium dioxide nanosheet through hydrogenation, a nano material taking titanium dioxide as a core and highly disordered titanium dioxide as a shell is formed on the nanosheet, the absorption of visible light and near infrared light is increased due to the introduction of defects, a new molecular orbit is generated in a band gap, the transfer of electrons is promoted, and the photocatalytic efficiency is greatly improved.
However, since the band gap of titanium dioxide is relatively large, only ultraviolet light can make electrons jump from the valence band to the conduction band, and the electrons and holes which jump out are easily recombined, which greatly reduces the photocatalytic efficiency of titanium dioxide, and therefore, it is extremely important to reduce the band gap of titanium dioxide and capture the electrons which jump.
Disclosure of Invention
The invention provides a preparation method of titanium dioxide oxidized by a photocatalyst, aiming at solving the technical problems that the band gap of titanium dioxide is larger, and electrons and holes which are jumped out are easy to combine, so that the photocatalytic efficiency of the titanium dioxide is reduced.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of titanium dioxide oxidized by a photocatalyst comprises the steps of oxidizing titanium dioxide by an oxidant, filtering, washing and drying to obtain an oxidized titanium dioxide photocatalyst; or reacting tetrabutyl phthalate with oxide in an autoclave, washing and drying, finally heating in a muffle furnace, cooling and grinding to obtain the oxidized titanium dioxide photocatalyst.
Further, the preparation method comprises the steps of mixing the potassium permanganate solution with the titanium dioxide, then carrying out ultrasonic oscillation to enable the potassium permanganate solution and the titanium dioxide to be uniformly dispersed, and stirring and refluxing for 12-24 hours at the temperature of 50-150 ℃. After the reaction is finished, centrifuging, washing for three times by using deionized water and ethanol, drying at 50-100 ℃, and grinding by using a mortar to obtain oxidized titanium dioxide;
or mixing titanium dioxide and potassium permanganate in a pulverizer, then placing in an oven to dry for 12-24h at 50-100 ℃, washing with deionized water and ethanol for three times after reaction, drying at 50-100 ℃, and grinding with a mortar to obtain oxidized titanium dioxide;
or adding titanium dioxide into a sulfuric acid solution with the mass fraction of 1% -98%, uniformly distributing by ultrasonic oscillation, heating and refluxing for 1-5h at 80-150 ℃, filtering, washing to be neutral by deionized water, drying at 50-100 ℃, and grinding by using a mortar to obtain oxidized titanium dioxide;
or, putting hydrogen peroxide solution into a quartz test tube, adding titanium dioxide into the quartz test tube, performing ultrasonic oscillation to uniformly disperse the titanium dioxide, irradiating the quartz test tube for 2 to 4 hours under a 100-500W mercury lamp, washing the quartz test tube for three times by using deionized water, drying the quartz test tube in an oven at 50 to 100 ℃, and grinding the quartz test tube to obtain oxidized titanium dioxide;
or sequentially adding sulfuric acid and a hydrogen peroxide solution into tetrabutyl phthalate, stirring for 30 minutes at room temperature, transferring the mixed solution into an autoclave with a polytetrafluoroethylene lining, reacting for 24 hours at 150 ℃, sequentially washing with deionized water and ethanol for three times after the reaction is finished, drying for 5 hours at 80 ℃ in an oven, finally heating for 2-4 hours at 500 ℃ in a muffle furnace, then cooling at room temperature, and grinding to obtain the titanium dioxide oxide.
Preferably, the mass fraction of the potassium permanganate solution is 1% -5%, and the volume mass ratio of the potassium permanganate solution to the titanium dioxide is 6 ml: 1g of the total weight of the composition.
Preferably, the mass ratio of the titanium dioxide to the potassium permanganate is 100: 1.
Preferably, the volume mass ratio of the sulfuric acid solution to the titanium dioxide is 6 ml: 1g of the total weight of the composition.
Preferably, the mass fraction of the hydrogen peroxide solution is 5% -10%, and the volume mass ratio of the hydrogen peroxide solution to the titanium dioxide is 10 ml: 1g of the total weight of the composition.
Preferably, the volume ratio of the tetrabutyl phthalate to the sulfuric acid solution to the hydrogen peroxide solution is 50:5: 40.
Further, the potassium permanganate can be replaced by other high-valence metal oxides, and the hydrogen peroxide solution can be replaced by potassium persulfate, an ammonium persulfate solution, oxygen or ozone.
Further, the other high-valence metal oxide is potassium dichromate.
The oxidized titanium dioxide prepared by the preparation method disclosed by the invention has potential application in the aspects of clean energy (such as hydrogen preparation), carbon-neutralized carbon circulation (such as carbon dioxide reduction), microorganisms, organic wastewater and the like.
Compared with the prior art, the invention has the following beneficial effects:
transition metal doped titanium dioxide has poor thermal stability, and once the structure is damaged, the number of carrier recombination centers is increased, and in addition, expensive ion implantation equipment is required. When the N-doped titanium dioxide and the black titanium dioxide are exposed in the air, O in the air2And H2O will quickly fill oxygen vacancies and defects, thereby reducing photocatalytic ability. The invention inserts extra oxygen into titanium dioxide crystal lattice by oxidation method, the prepared oxidized titanium dioxide has excellent thermal stability, long quality guarantee period, simple preparation method and low cost, and compared with pure titanium dioxide, the oxidized titanium dioxide has higher photocatalytic activity under ultraviolet light and visible light.
Drawings
FIG. 1 is a UV-vis diffuse reflectance spectrum of titanium dioxide and oxidized titanium dioxide.
FIG. 2 is an XPS high resolution spectrum of titania and titania, wherein a is titania Ti2p, b is titania Ti2p, c is titania O1s, d is titania O1s, and e is an XPS valence band spectrum.
FIG. 3 is a DOS plot of titania and titania, where a is the total DOS plot, b is the partial DOS plot of titania, and c is the partial DOS plot of titania.
FIG. 4 is a HRTEM image of titania and oxidized titania, where a is titania and b is oxidized titania.
FIG. 5 is a graph of UV-Vis absorption in different time periods of simulated degradation of dye wastewater (methyl orange).
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Preparing 1-5% by mass potassium permanganate aqueous solution, taking a 100mL flask, adding the 30mL potassium permanganate solution and 5g titanium dioxide, uniformly dispersing by ultrasonic oscillation, and stirring and refluxing for 24h at 80 ℃. After the reaction is finished, centrifuging, washing for three times by using deionized water and ethanol, drying at 60 ℃, and grinding by using a mortar to obtain the titanium dioxide oxide. The potassium permanganate can be replaced by high valence metal oxide such as potassium dichromate.
Example 2
And (2) fully mixing 10g of titanium dioxide and 0.1g of potassium permanganate in a grinder, then placing the mixture in an oven to dry for 24 hours at 80 ℃, washing the mixture for three times by using deionized water and ethanol after the reaction is finished, drying the mixture at 60 ℃, and grinding the mixture by using a mortar to obtain the oxidized titanium dioxide. The potassium permanganate can be replaced by high valence metal oxide such as potassium dichromate.
Example 3
Adding 30mL of 1% -98% dilute sulfuric acid solution or concentrated sulfuric acid solution into a 250mL flask, adding 5g of titanium dioxide, uniformly distributing by ultrasonic oscillation, heating and refluxing for 12h at 80-150 ℃, filtering, washing to be neutral by deionized water, drying at 80 ℃, and grinding by using a mortar to obtain the titanium dioxide oxide.
Example 4
Adding 5g of titanium dioxide into 50mL of 5% -10% hydrogen peroxide solution in an 80mL quartz test tube, uniformly dispersing by ultrasonic oscillation, irradiating for 2h under a 500W mercury lamp, washing with deionized water for three times, drying in an oven at 80 ℃, and grinding to obtain the oxidized titanium dioxide. The hydrogen peroxide solution can be replaced by 5-10% of potassium persulfate, ammonium persulfate solution, oxygen and ozone.
Example 5
Taking 50mL of tetrabutyl phthalate, sequentially adding 5mL of sulfuric acid and 40mL of hydrogen peroxide solution with the mass fraction of 10%, stirring for 30 minutes at room temperature, transferring the mixed solution into a 150mL of autoclave with a polytetrafluoroethylene lining, reacting for 24 hours at 150 ℃, sequentially washing with deionized water and ethanol for three times after the reaction is finished, drying for 5 hours at 80 ℃ in an oven, finally heating for 2 hours at 500 ℃ in a muffle furnace, then cooling at room temperature, and grinding to obtain titanium dioxide oxide.
Instrumental detection
The light absorption properties of titanium dioxide and oxidized titanium dioxide were analyzed using an ultraviolet spectrophotometer. The ultraviolet and visible light absorption spectrum shows that the titanium dioxide can only absorb light below 400nm, and the titanium dioxide after oxidation treatment can absorb light between 400nm and 600nm (see figure 1). This indicates that the oxidation treatment of titanium dioxide can shift its light absorption ability from ultraviolet light to visible light.
The XPS valence band spectrum (see FIG. 2 e) shows that at the top of the valence band, the oxidized titanium dioxide shows new electronic states which extend the valence band of the titanium dioxide into the forbidden band, allowing electrons to pass throughThe transition from the valence band top to the conduction band is easier, and the utilization rate of the titanium dioxide to visible light is improved. HRTEM (see fig. 4) images show that the 101 lattice spacing of anatase (approximately equal to 0.36 nm) and the atomic layers on the surface become disordered and hazy compared to pure titanium dioxide. This indicates that the insertion of oxygen causes the lattice of titanium dioxide to become disordered, a new electron capture center is generated, and the probability of electron hole recombination is reduced. X-ray photoelectron spectroscopy is used to determine the elemental composition and chemical valence state of oxidized titanium dioxide, and the high resolution spectrum of O1s of titanium dioxide has a peak at 529.70eV, and this absorption peak is generated by O in the titanium dioxide crystal lattice. (see FIG. 2 d) however, for oxidized titania, O1s shows two absorption peaks 532.23 eV and 529.86 eV, 532.23 eV being due to the insertion of O into the lattice, forming a Ti-O-O bond. (see FIG. 2c) the absorption peaks of Ti2p 1/2 and Ti2p 3/2 of pure titanium dioxide are at 464.28 eV and 458.58 eV, which are in contrast to the Ti in titanium dioxide4+Correspondingly, but the Ti2p 1/2 and Ti2p 3/2 peaks of the oxidized titania shifted toward the high bond energy because the insertion of oxygen changed the Ti-O-Ti to Ti-O-Ti.
VASP simulation calculation:
the electronic structure of titania oxide and titania was studied using DFT-based first-order principles. The valence band top of pure titanium dioxide consists primarily of O2p and the valence band bottom consists primarily of Ti3d (see fig. 3). From fig. 2, it can be seen that the band gap of the oxidized titania is reduced compared to that of pure titania. And three new electronic states appear at the top and bottom of the valence band, among which the electronic state at-1 eV and-0.25 eV is mainly composed of O2p, and the electronic state at 0.57eV at the bottom of the conduction band is mainly composed of O2p hybridized with Ti3d (see fig. 3). This shows that new electronic states appear in the band gap due to the insertion of oxygen, and they can be used to capture electrons, thereby inhibiting the recombination of electrons and holes, improving the photocatalytic efficiency, and at the same time, the reduction of the band gap means that the oxidized titanium dioxide can utilize visible light of more than 400nm, and the calculation result is consistent with the experimental result.
Simulation degradation wastewater test:
the degradation of organic wastewater is simulated by taking a simulated degradation methyl orange solution as a case, and pure titanium dioxide is used as a contrast, and the oxidized titanium dioxide shows excellent photochemical reactivity under the irradiation of ultraviolet light (simulation of a high-pressure mercury lamp) or sunlight (simulation of a xenon lamp). Under the irradiation of simulated sunlight, the degradation rate of oxidized titanium dioxide for degrading methyl orange can reach 85.57 percent after 105 min, and pure titanium dioxide can only reach 36.33 percent in the same time. Under the irradiation of an ultraviolet lamp, the degradation rate of the oxidized titanium dioxide reaches 99.85% in 21min, while the degradation rate of the common titanium dioxide reaches 95.93% after 60min of illumination.
Claims (10)
1. A preparation method of titanium dioxide oxidized by a photocatalyst is characterized in that the titanium dioxide is oxidized by an oxidant, and then the oxidized titanium dioxide photocatalyst is prepared by filtering, washing and drying; or reacting tetrabutyl phthalate with oxide in an autoclave, washing and drying, finally heating in a muffle furnace, cooling and grinding to obtain the oxidized titanium dioxide photocatalyst.
2. The method for preparing titanium dioxide by photocatalyst oxidation according to claim 1, wherein the preparation method comprises mixing potassium permanganate solution with titanium dioxide, then ultrasonically oscillating to disperse the potassium permanganate solution uniformly, and stirring and refluxing at 50-150 ℃ for 12-24 h;
after the reaction is finished, centrifuging, washing for three times by using deionized water and ethanol, drying at 50-100 ℃, and grinding by using a mortar to obtain oxidized titanium dioxide;
or mixing titanium dioxide and potassium permanganate in a pulverizer, then placing in an oven to dry for 12-24h at 50-100 ℃, washing with deionized water and ethanol for three times after reaction, drying at 50-100 ℃, and grinding with a mortar to obtain oxidized titanium dioxide;
or adding titanium dioxide into a sulfuric acid solution with the mass fraction of 1% -98%, uniformly distributing by ultrasonic oscillation, heating and refluxing for 1-5h at 80-150 ℃, filtering, washing to be neutral by deionized water, drying at 50-100 ℃, and grinding by using a mortar to obtain oxidized titanium dioxide;
or, putting hydrogen peroxide solution into a quartz test tube, adding titanium dioxide into the quartz test tube, performing ultrasonic oscillation to uniformly disperse the titanium dioxide, irradiating the quartz test tube for 2 to 4 hours under a 100-500W mercury lamp, washing the quartz test tube for three times by using deionized water, drying the quartz test tube in an oven at 50 to 100 ℃, and grinding the quartz test tube to obtain oxidized titanium dioxide;
or sequentially adding sulfuric acid and a hydrogen peroxide solution into tetrabutyl phthalate, stirring at room temperature for 30-60 minutes, transferring the mixed solution into an autoclave with a polytetrafluoroethylene lining, reacting at 150-180 ℃ for 24 hours, sequentially washing with deionized water and ethanol for three times after the reaction is finished, drying in an oven at 50-100 ℃ for 5 hours, finally heating in a muffle furnace at 500 ℃ for 2-4 hours, then cooling at room temperature, and grinding to obtain the titanium dioxide oxide.
3. The preparation method of titanium dioxide oxidized by a photocatalyst according to claim 2, wherein the mass fraction of the potassium permanganate solution is 1% -5%, and the volume mass ratio of the potassium permanganate solution to the titanium dioxide is 6 ml: 1g of the total weight of the composition.
4. The method for preparing titanium dioxide by photocatalytic oxidation according to claim 2, wherein the mass ratio of titanium dioxide to potassium permanganate is 100: 1.
5. The method for preparing titania by photocatalyst according to claim 2, wherein the volume-to-mass ratio of sulfuric acid solution to titania is 6 ml: 1g of the total weight of the composition.
6. The method for preparing titanium dioxide by photocatalytic oxidation according to claim 2, wherein the mass fraction of the hydrogen peroxide solution is 5% -10%, and the volume mass ratio of the hydrogen peroxide solution to the titanium dioxide is 10 ml: 1g of the total weight of the composition.
7. The method of claim 2, wherein the volume ratio of tetrabutyl phthalate, the sulfuric acid solution and the hydrogen peroxide solution is 50:5: 40.
8. The method for preparing titania by photocatalyst oxidation according to any one of claims 2 to 7, wherein potassium permanganate is replaced by other metal oxide of high valence, and the hydrogen peroxide solution is replaced by potassium persulfate, ammonium persulfate solution, oxygen or ozone.
9. The method of claim 8, wherein the other high valence metal oxide is potassium dichromate.
10. Use of the oxidized titanium dioxide prepared by the method of any one of claims 1 to 7 for cleaning energy, carbon-neutral carbon cycle, and microbial and organic wastewater.
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