CN114588920A - Boron carbide doped titanium dioxide photocatalyst, preparation method and application thereof - Google Patents
Boron carbide doped titanium dioxide photocatalyst, preparation method and application thereof 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 117
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 96
- 229910052580 B4C Inorganic materials 0.000 title claims abstract description 45
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 37
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000084 colloidal system Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000002351 wastewater Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001868 water Inorganic materials 0.000 claims abstract description 17
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 12
- 238000001223 reverse osmosis Methods 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 18
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 6
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 6
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 229910003460 diamond Inorganic materials 0.000 description 5
- 239000010432 diamond Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000011895 specific detection Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
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- 150000003384 small molecules Chemical class 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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—
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/34—Organic compounds containing oxygen
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- 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
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- 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
- C02F2101/40—Organic compounds containing sulfur
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a boron carbide doped titanium dioxide photocatalyst, a preparation method and application thereof, and belongs to the technical field of photocatalysts. The photocatalyst consists of B4C and TiO2According to the mass ratio of 1 (5-100), and B4C supported on TiO2The above step (1); the TiO is2The crystal form of (A) is anatase type. B is to be4C is dispersed in TiO taking tetrabutyl titanate as raw material2Mixing the precursor solution to obtain a mixed systemAdding water, stirring until colloid is obtained, aging the colloid, drying, and grinding into powder; and calcining the powder to obtain the photocatalyst. The photocatalyst is used for treating organic wastewater. The photocatalyst can utilize visible light, so that the photocatalytic performance of the photocatalyst is improved, and the photocatalyst can well degrade organic pollutants in organic wastewater.
Description
Technical Field
The invention relates to a boron carbide doped titanium dioxide photocatalyst, a preparation method and application thereof, and belongs to the technical field of photocatalysts.
Background
The photocatalytic oxidation method is one of new research hotspots in the field of environmental science and engineering at present, and is suitable for treating organic wastewater difficult to degrade. The photocatalytic oxidation method is to utilize sunlight to degrade harmful pollutant in the presence of photocatalyst to convert the harmful pollutant into CO2、H2O or other small molecule substances. The photocatalytic oxidation method has the characteristics of mild reaction conditions, high treatment efficiency, high reaction speed, wide application range, environmental friendliness, low secondary pollution and the like, and has a good application prospect.
Titanium dioxide (TiO)2) As an n-type semiconductor material, the material has wide source and low price, and shows great application potential with higher photocatalytic activity and stable chemical performance. TiO 22There are four types of titanium dioxide, anatase type, rutile type, brookite type, and bronze type.
Anatase phase TiO2Is an ideal semiconductor photocatalysis material, and compared with other semiconductor materials, the anatase phase TiO2Has the advantages of low price, simple preparation, stable chemical performance and the like. Anatase phase TiO2One of the preparation methods of (a) is a sol-gel method.
TiO2Belonging to wide-gap n-type semiconductors, the two main crystals have a gap of 3.2eV (anatase) and 3.0eV (rutile), respectively, which means that only under the irradiation of uv light can the photogenerated electrons be excited to transit to the conduction band and finally initiate a photochemical reaction with the contaminant. For natural sunlight, the visible light occupies 45% of sunlight, while the ultraviolet light is only 3% -5%. It is known that most natural light cannot be absorbed by TiO2Effectively utilizes and greatly limits TiO2Application as a photocatalyst.
Disclosure of Invention
In view of the above, the present invention provides a boron carbide doped titanium dioxide photocatalyst, and preparation and application thereof. By using B4C doping for TiO2Modification of (2), p-type B4C and n type anatase TiO2The heterojunction structure is formed, the utilization rate of the prepared photocatalyst on visible light is improved, and the photocatalytic performance of the photocatalyst is improved.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A boron carbide doped titanium dioxide photocatalyst consisting of boron carbide (B)4C) And titanium dioxide (TiO)2) According to the mass ratio of 1 (5-100), and B4C supported on TiO2The above step (1); the TiO is2The crystal form of (A) is anatase type.
The invention relates to a preparation method of a boron carbide doped titanium dioxide photocatalyst, which comprises the following steps:
(1) preparation of TiO2Precursor solution: adding tetrabutyl titanate into absolute ethyl alcohol under the condition of stirring, adding glacial acetic acid to prevent tetrabutyl titanate from hydrolyzing, and uniformly stirring at the temperature of 25 +/-5 ℃ to obtain TiO2And (3) precursor solution.
(2) To TiO 22Adding B into the precursor solution4C powder is evenly stirred and then ultrasonic oscillation treatment is carried out to lead B powder to be4Powder C in TiO2The precursor solution is dispersed more uniformly to obtain a mixed system.
(3) Hydrolysis: adding water into the mixed system, and stirring until colloid is formed, wherein the colloid is loaded with B4TiO of C2And (3) colloid.
(4) Aging: and standing the colloid to obtain the aged colloid.
(5) And (3) drying: the aged gel was dried and then ground into a powder.
(6) And (3) calcining: calcining the powder at 400-500 ℃ for 2-4 h to obtain the boron carbide doped titanium dioxide photocatalyst.
Preferably, the volume ratio of the absolute ethyl alcohol to the tetrabutyl titanate to the glacial acetic acid is (3-6): 1.5-3): 1-2.
Preferably, in step (2), B4The particle size distribution of the C powder is 1-10 μm.
Preferably, in the step (2), the ultrasonic vibration treatment is carried out for 10min to 15 min.
Preferably, in the step (4), the colloid is kept stand for 8 to 12 hours at the temperature of 25 +/-5 ℃.
Preferably, in the step (5), the drying is carried out for 12 to 36 hours at a temperature of between 90 and 120 ℃.
The application of the boron carbide doped titanium dioxide photocatalyst is to use the photocatalyst in the treatment of organic wastewater.
Preferably, the specific method for application comprises the following steps: adding the photocatalyst into organic wastewater, stirring under the condition of light, and carrying out photocatalytic oxidation reaction.
More preferably, the organic wastewater is reverse osmosis concentrated water, and the organic pollutant is an isothiazolinone organic pollutant.
More preferably, 1L of organic wastewater is treated by 1g to 4g of the photocatalyst at the temperature of 25 ℃ to 45 ℃, namely, the adding amount of the photocatalyst is 1g/L to 4g/L, the concentration of organic pollutants in the organic wastewater is more than 0 and less than or equal to 200mg/L, and the reaction time is less than or equal to 6h, so that the organic pollutants in the organic wastewater can be removed.
More preferably, the rotation speed of the stirring is 150rpm to 200 rpm.
Advantageous effects
The invention provides a boron carbide doped titanium dioxide photocatalyst, and B doped in the photocatalyst4C supported on TiO2Upper, B4The structure of the C icosahedron shows strong absorption in the full solar spectrum, improves the electron transmission effect, and passes through TiO2And B4The asymmetric heterojunction structure formed by the C enhances the carrier separation and improves the stability and the dispersibility of the inner core. Thus B4C and anatase TiO2The interface coupling effect between the two can remarkably promote the light-excited charge separation. The photocatalyst and the photocatalyst T of the inventioniO2In contrast, the photocatalyst showed strong absorption in the same UV-visible region, indicating that the inventive photocatalyst consisting of B4C modified TiO2The visible light absorption of the catalyst is improved, and the photocatalytic performance is obviously improved. And with TiO2Compared with the prior art, the photocatalyst has the characteristics of corrosion resistance, high temperature resistance, high strength, remarkable economical efficiency and the like, and is particularly suitable for treating organic wastewater because B4The photocatalyst C has the characteristics of low density, high strength, good high-temperature stability and chemical stability and the like, so that the photocatalyst can not cause secondary pollution to a water body.
The invention provides a preparation method of a boron carbide doped titanium dioxide photocatalyst, which takes tetrabutyl titanate as a raw material, adopts a sol-gel method to prepare the photocatalyst, and B4The C powder is dispersed into tetrabutyl titanate to form a mixed system, uniform doping on a molecular level is realized in a short time, the preparation method is simple and easy to operate, the raw materials are easy to obtain, and the cost is low. The ultrasonic vibration treatment in the preparation method can enable B to be4Powder C in TiO2The dispersion in the precursor solution is more uniform, which is beneficial to improving the photocatalytic performance of the prepared photocatalyst.
The invention provides an application of a boron carbide doped titanium dioxide photocatalyst, and the photocatalyst has a good treatment effect on organic wastewater; further, the photocatalyst can remove organic pollutants in the wastewater under a mild condition, the removal effect is good, the temperature range is about 25-45 ℃ under the irradiation of a light source with the wavelength range of 390-780 nm, isothiazolinone wastewater with the concentration of less than or equal to 200mg/L reacts for about 6 hours under the condition that the adding amount of the photocatalyst is 1-4 g/L, the removal rate of the isothiazolinone organic pollutants can reach more than 90%, and the photocatalyst has good photocatalytic performance.
Drawings
FIG. 1 is an SEM image at 3000 times magnification of the photocatalyst obtained in example 2.
Fig. 2 is an SEM image of the photocatalyst prepared in example 2 at a magnification of 5000.
Detailed Description
The invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available or may be prepared from literature.
Example 1
(1) Adding 60mL of absolute ethyl alcohol serving as a solvent into a beaker for magnetic stirring, slowly adding 20mL of tetrabutyl titanate into the absolute ethyl alcohol, continuously stirring for 30min at 25 +/-5 ℃, adding 10mL of glacial acetic acid, preventing hydrolysis, and uniformly stirring to obtain TiO2And (3) precursor solution.
(2) To TiO 22Adding B with the particle size distribution of 1-10 mu m into the precursor solution4C powder, wherein, B4C and TiO2The mass ratio of (1: 100) and fully stirring for 15 min; and then placing the mixture into an ultrasonic oscillator to vibrate for 10min to obtain a mixed system.
(3) Slowly adding 6mL of deionized water into the mixed system, stirring for 30min to form colloid, and stopping stirring to obtain the load B4TiO of C2And (3) colloid.
(4) Will be loaded with B4TiO of C2The colloid was allowed to stand at 25 + -5 deg.C for 10h to give a gray-black aged colloid.
(5) And (3) putting the aged colloid into a constant-temperature drying box, drying at 120 ℃ for 12h, taking out, and grinding into powder.
(6) And (3) placing the powder in a muffle furnace, and calcining for 2h at 500 ℃ to obtain the boron carbide doped titanium dioxide photocatalyst.
The prepared photocatalyst is subjected to morphology characterization by a JSM-7500F field emission scanning electron microscope of Japan electronic Co., Ltd, and a test result shows that the photocatalyst is in a multi-face diamond structure.
Example 2
(1) Adding 60mL of absolute ethyl alcohol serving as a solvent into a beaker for magnetic stirring, slowly adding 20mL of tetrabutyl titanate into the absolute ethyl alcohol, continuously stirring for 30min at 25 +/-5 ℃, adding 10mL of glacial acetic acid to prevent hydrolysis, and uniformly stirringTo obtain TiO2And (3) precursor solution.
(2) To TiO 22Adding B with the particle size distribution of 1-10 mu m into the precursor solution4C powder of B4C and TiO2The mass ratio of (1: 20) and fully stirring for 15 min; then placing the mixture into an ultrasonic oscillator to vibrate for 15 min; a mixed system is obtained.
(3) Slowly adding 6mL of deionized water into the mixed system, stirring for 30min to form colloid, and stopping stirring to obtain the load B4TiO of C2And (3) colloid.
(4) Will be loaded with B4TiO of C2The colloid was allowed to stand at 25 + -5 deg.C for 12h to give a gray-black aged colloid.
(5) And (3) putting the aged colloid into a constant-temperature drying box, drying at 90 ℃ for 36h, taking out, and grinding into powder.
(6) And (3) placing the powder in a muffle furnace, and calcining for 4h at 400 ℃ to obtain the boron carbide doped titanium dioxide photocatalyst.
The obtained photocatalyst was morphologically characterized by using a JSM-7500F field emission scanning electron microscope of japan electronics corporation, and the photocatalyst showed a polyhedral diamond structure as shown in fig. 1 and 2.
Example 3
Unlike example 2, in step (2), B4C and TiO2The mass ratio of (A) to (B) is 1: 15; the rest is the same as the embodiment 2; obtaining the boron carbide doped titanium dioxide photocatalyst.
The prepared photocatalyst is subjected to shape characterization by using a JSM-7500F field emission scanning electron microscope of Japan electronic Co., Ltd, and a test result shows that the photocatalyst is in a multi-face diamond structure.
Example 4
Unlike example 2, in step (2), B4C and TiO2The mass ratio of (A) to (B) is 1: 10; the rest is the same as the embodiment 2; obtaining the boron carbide doped titanium dioxide photocatalyst.
The prepared photocatalyst is subjected to shape characterization by using a JSM-7500F field emission scanning electron microscope of Japan electronic Co., Ltd, and a test result shows that the photocatalyst is in a multi-face diamond structure.
Example 5
Unlike example 2, in step (2), B4C and TiO2The mass ratio of (A) to (B) is 1: 5; the rest is the same as the embodiment 2; obtaining the boron carbide doped titanium dioxide photocatalyst.
The prepared photocatalyst is subjected to shape characterization by using a JSM-7500F field emission scanning electron microscope of Japan electronic Co., Ltd, and a test result shows that the photocatalyst is in a multi-face diamond structure.
Example 6
The boron carbide doped titanium dioxide photocatalyst prepared in example 2 is taken as a representative, and the removal effect of the photocatalyst on organic pollutants in reverse osmosis concentrated water under different treatment times is detected. Common isothiazolinone organic pollutants in reverse osmosis concentrated water are used as model pollutants, and the specific detection steps are as follows:
(1) adding the boron carbide-doped titanium dioxide photocatalyst prepared in example 2 to an aqueous solution I containing 1, 2-benzisothiazolin-3-one (BIT), an aqueous solution II containing 2-methyl-4-isothiazolin-3-one (MIT), and an aqueous solution III containing 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), respectively, to obtain mixed solutions; wherein the concentration of BIT in the aqueous solution I is 200mg/L, the concentration of MIT in the aqueous solution II is 200mg/L, and the concentration of CMIT in the aqueous solution III is 200 mg/L; 1L of the aqueous solution I, the aqueous solution II and the aqueous solution III are treated, and the dosage of the photocatalyst is 1 g.
(2) Putting the mixed solution prepared in the step (1) into a 200W xenon lamp photocatalytic box, wherein the wavelength range of a xenon lamp is 390-780 nm, stirring the mixed solution prepared in the step (1) in a magnetic stirring mode to perform photocatalytic oxidation reaction, wherein the stirring speed is 150rpm, the temperature of the photocatalytic oxidation reaction can gradually rise due to the irradiation of the xenon lamp, the reaction temperature range is about 25-45 ℃, taking out the mixed solution when the reaction time is 30min, 60min, 90min, 120min, 180min and 360min, filtering to realize solid-liquid separation, and taking out the filtered solution for detection.
The detection is that a UV-8000 ultraviolet-visible spectrophotometer is adopted to measure the ultraviolet absorbance of the filtered solution, and the contents of BIT, CMIT and MIT can be respectively measured at 317nm, 275nm and 273 nm. The ultraviolet absorbance is used for reacting the removal rate of the isothiazolinone organic pollutants in the reverse osmosis concentrated water of the photocatalyst prepared in the example 2 under different treatment times, and the test results are shown in the table 1:
TABLE 1 removal rate of isothiazolinone organic pollutants by the photocatalyst under different reaction times
| Time (min) | 0 | 30 | 60 | 90 | 120 | 180 | 360 |
| Removal ratio of BIT (%) | 0 | 14.04 | 28.32 | 45.38 | 74.51 | 86.26 | 97.12 |
| Removal rate of CMIT (%) | 0 | 20.04 | 29.24 | 51.07 | 76.05 | 85.58 | 98.26 |
| MIT removal Rate (%) | 0 | 6.75 | 12.85 | 23.74 | 38.5 | 47.52 | 96.53 |
As can be seen from Table 1, in the process of carrying out catalytic oxidative degradation on isothiazolinone organic pollutants in reverse osmosis concentrated water by using the photocatalyst, the removal rate of the isothiazolinone organic pollutants is increased along with the increase of time, and the removal rates of BIT, CMIT and MIT are all more than 90% at 6 h. The boron carbide doped titanium dioxide photocatalyst prepared in other examples has similar removal effect on isothiazolinone organic pollutants in reverse osmosis concentrated water.
Example 7
The boron carbide doped titanium dioxide photocatalyst prepared in example 5 was used as a representative, and the removal effect of the photocatalyst on organic pollutants in reverse osmosis concentrated water was examined at different dosages. Common isothiazolinone organic pollutants in reverse osmosis concentrated water are used as model pollutants, and the specific detection steps are as follows:
(1) adding the boron carbide doped titanium dioxide photocatalyst prepared in example 5 into 5 parts of an aqueous solution IV containing 2-methyl-4-isothiazolin-3-one (MIT) respectively to obtain mixed solutions; wherein, the concentration of MIT in 5 parts of the aqueous solution IV is 200mg/L, 1L of the aqueous solution IV is processed, and the dosage of the photocatalyst is 0.2g, 1g, 2g, 3g and 4g in sequence.
(2) Putting the mixed solution prepared in the step (1) into a 200W xenon lamp photocatalytic box, wherein the wavelength range of a xenon lamp is 390-780 nm, stirring the mixed solution prepared in the step (1) in a magnetic stirring mode to perform photocatalytic oxidation reaction, wherein the stirring speed is 150rpm, the temperature of the photocatalytic oxidation reaction can gradually rise due to the irradiation of the xenon lamp, the reaction temperature range is about 25-45 ℃, when the reaction time is 30min, 60min, 90min, 120min, 180min and 360min, taking out the mixed solution, filtering to realize solid-liquid separation, and taking out the filtered solution for detection.
And the detection comprises the steps of measuring the ultraviolet absorbance of the filtered solution by using a UV-8000 ultraviolet-visible spectrophotometer and measuring the MIT content at 273 nm. The ultraviolet absorbance was used to reflect the removal rate of the photocatalyst prepared in example 5 on MIT in reverse osmosis concentrated water at different dosages and treatment times, and the test results are shown in table 2:
TABLE 2 removal rate of MIT by the photocatalyst at different dosages and treatment times
| Time (min) | 0 | 30 | 60 | 90 | 120 | 180 | 360 |
| Removal rate (%) of 0.2g/L | 0 | 1.50 | 2.16 | 2.69 | 3.41 | 3.57 | 63.58 |
| Removal ratio (%) of 1g/L | 0 | 5.58 | 11.87 | 18.62 | 26.38 | 38.43 | 96.07 |
| Removal ratio (%) of 2g/L | 0 | 10.40 | 22.83 | 38.45 | 51.82 | 82.66 | 98.86 |
| Removal ratio (%) of 3g/L | 0 | 16.55 | 39.38 | 55.34 | 69.95 | 92.01 | — |
| Removal ratio (%) of 4g/L | 0 | 20.00 | 44.81 | 61.88 | 79.78 | 97.30 | — |
As is clear from Table 2, the modified TiO produced in example 52In the photocatalytic oxidation degradation process of the photocatalyst, the addition amount of the photocatalyst is in the range of 0.2 g/L-4 g/L in the photocatalytic oxidation degradation process of MIT in reverse osmosis concentrated water, the removal rate of MIT is increased along with the increase of the treatment dosage of the photocatalyst, and the removal rate of MIT is also increased along with the increase of the treatment time. The addition amount of the photocatalyst is in the range of 1 g/L-4 g/L, and the removal rate of MIT reaches more than 90% in 6 h. And when the adding amount of the photocatalyst is 3g/L and 4g/L, the removal rate of the photocatalyst to MIT can reach more than 90% at 3h, so that the removal rate of the photocatalyst to MIT at 6h is not continuously tested. The boron carbide doped titanium dioxide photocatalyst prepared in other examples has similar removal effect on isothiazolinone organic pollutants in reverse osmosis concentrated water.
The present invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the principle of the present invention should be considered within the scope of the present invention.
Claims (10)
1. A boron carbide doped titanium dioxide photocatalyst is characterized in that: the photocatalyst consists of B4C and TiO2According to the mass ratio of 1 (5-100), and B4C supported on TiO2The above step (1); the TiO is2The crystal form of (A) is anatase type.
2. A method of preparing the boron carbide doped titanium dioxide photocatalyst of claim 1, wherein: the method comprises the following steps:
(1) adding tetrabutyl titanate into absolute ethyl alcohol under the condition of stirring, adding glacial acetic acid to prevent tetrabutyl titanate from hydrolyzing, and uniformly stirring at the temperature of 25 +/-5 ℃ to obtain TiO2Precursor solution;
(2) to TiO 22Adding B into the precursor solution4C, uniformly stirring the powder C, and then carrying out ultrasonic oscillation treatment to obtain a mixed system;
(3) adding water into the mixed system, and stirring until a colloid is formed, wherein the colloid is loaded with B4TiO of C2A colloid;
(4) standing the colloid to obtain an aged colloid;
(5) drying the aged colloid, and grinding into powder;
(6) calcining the powder at 400-500 ℃ for 2-4 h to obtain the boron carbide doped titanium dioxide photocatalyst.
3. The method for preparing a boron carbide doped titanium dioxide photocatalyst according to claim 2, characterized in that: the volume ratio of the absolute ethyl alcohol to the tetrabutyl titanate to the glacial acetic acid is (3-6) to (1.5-3) to (1-2).
4. The method for preparing a boron carbide-doped titanium dioxide photocatalyst according to claim 2, wherein: b is4The particle size distribution of the C powder is 1-10 μm.
5. The method for preparing a boron carbide-doped titanium dioxide photocatalyst according to claim 2, wherein: in the step (2), carrying out ultrasonic oscillation treatment for 10-15 min;
in the step (4), standing the colloid for 8-12 h at the temperature of 25 +/-5 ℃;
in the step (5), the drying is carried out for 12 to 36 hours at the temperature of between 90 and 120 ℃.
6. The method for preparing a boron carbide-doped titanium dioxide photocatalyst according to claim 2, wherein: in the step (1), the volume ratio of the absolute ethyl alcohol to the tetrabutyl titanate to the glacial acetic acid is (3-6) to (1.5-3) to (1-2);
in the step (2), B is4The particle size distribution of the C powder is 1-10 mu m; ultrasonic vibration treatment is carried out for 10min to 15 min;
in the step (4), standing the colloid for 8-12 h at the temperature of 25 +/-5 ℃;
in the step (5), the drying is carried out for 12 to 36 hours at the temperature of between 90 and 120 ℃.
7. Use of the boron carbide doped titanium dioxide photocatalyst of claim 1, wherein: the photocatalyst is used for treating organic wastewater.
8. Use of the boron carbide doped titanium dioxide photocatalyst of claim 7, wherein: the specific method of the application comprises the following steps: adding the photocatalyst into organic wastewater, stirring under the condition of light, and carrying out photocatalytic oxidation reaction.
9. Use of the boron carbide doped titanium dioxide photocatalyst of claim 8, wherein: 1L of organic wastewater is treated by 1 g-4 g of the photocatalyst at the temperature of 25-45 ℃, the concentration of organic pollutants in the organic wastewater is more than 0 and less than or equal to 200mg/L, the reaction time is less than or equal to 6h, and the removal of the organic pollutants in the organic wastewater can be realized.
10. Use of the boron carbide doped titanium dioxide photocatalyst of claim 9, wherein: the organic wastewater is reverse osmosis concentrated water; the organic pollutants are isothiazolinone organic pollutants; the rotating speed of the stirring is 150 rpm-200 rpm.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004267985A (en) * | 2003-03-12 | 2004-09-30 | Sumitomo Electric Fine Polymer Inc | Photocatalyst carrier and method for producing the same |
| CN101721990A (en) * | 2009-12-04 | 2010-06-09 | 天津大学 | Method for preparing double rare-earth elements La and Y doped TiO2 photocatalyst |
| CN101773841A (en) * | 2010-01-29 | 2010-07-14 | 苏州科技学院 | Photocatalyst for water treatment |
| US20110003684A1 (en) * | 2004-11-16 | 2011-01-06 | Walid Abdelhemld Daoud | Method for making single-phase anatase titanium oxide |
| CN101972639A (en) * | 2010-09-30 | 2011-02-16 | 中国石油大学(华东) | Method for preparing high-activity titanium dioxide photocatalyst by using segmental calcination method |
| CN102491414A (en) * | 2011-11-30 | 2012-06-13 | 姚敏 | Preparation method of titanium dioxide (TiO2) photocatalyst |
| CN102784636A (en) * | 2012-07-17 | 2012-11-21 | 上海交通大学 | Preparation method of spherical gadolinium-doped titanium dioxide photocatalyst |
| CN103285846A (en) * | 2013-06-07 | 2013-09-11 | 西北工业大学 | Modified titanium dioxide/bamboo charcoal composite material and method for decoloring dye wastewater in sunlight |
| CN104353477A (en) * | 2014-11-26 | 2015-02-18 | 济源职业技术学院 | P-n heterojunction type visible light catalyst B4C/TiO2 and preparation method thereof |
| CN104923203A (en) * | 2015-05-20 | 2015-09-23 | 上海应用技术学院 | Composite photlocatalyst and preparation method as well as application thereof |
| CN114132959A (en) * | 2021-11-15 | 2022-03-04 | 武汉科技大学 | Core-shell structure B4C@TiO2Composite powder and preparation method thereof |
-
2022
- 2022-03-08 CN CN202210228202.6A patent/CN114588920A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004267985A (en) * | 2003-03-12 | 2004-09-30 | Sumitomo Electric Fine Polymer Inc | Photocatalyst carrier and method for producing the same |
| US20110003684A1 (en) * | 2004-11-16 | 2011-01-06 | Walid Abdelhemld Daoud | Method for making single-phase anatase titanium oxide |
| CN101721990A (en) * | 2009-12-04 | 2010-06-09 | 天津大学 | Method for preparing double rare-earth elements La and Y doped TiO2 photocatalyst |
| CN101773841A (en) * | 2010-01-29 | 2010-07-14 | 苏州科技学院 | Photocatalyst for water treatment |
| CN101972639A (en) * | 2010-09-30 | 2011-02-16 | 中国石油大学(华东) | Method for preparing high-activity titanium dioxide photocatalyst by using segmental calcination method |
| CN102491414A (en) * | 2011-11-30 | 2012-06-13 | 姚敏 | Preparation method of titanium dioxide (TiO2) photocatalyst |
| CN102784636A (en) * | 2012-07-17 | 2012-11-21 | 上海交通大学 | Preparation method of spherical gadolinium-doped titanium dioxide photocatalyst |
| CN103285846A (en) * | 2013-06-07 | 2013-09-11 | 西北工业大学 | Modified titanium dioxide/bamboo charcoal composite material and method for decoloring dye wastewater in sunlight |
| CN104353477A (en) * | 2014-11-26 | 2015-02-18 | 济源职业技术学院 | P-n heterojunction type visible light catalyst B4C/TiO2 and preparation method thereof |
| CN104923203A (en) * | 2015-05-20 | 2015-09-23 | 上海应用技术学院 | Composite photlocatalyst and preparation method as well as application thereof |
| CN114132959A (en) * | 2021-11-15 | 2022-03-04 | 武汉科技大学 | Core-shell structure B4C@TiO2Composite powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 孟前进等: "TiO2粉体的溶胶-凝胶法制备及表征", 《化工技术与开发》 * |
| 熊智信等: "锐钛矿型TiO2光催化降解异噻唑啉酮废水研究", 《环境科学学报》 * |
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