CN113262818A - PVP-Si @ TiO applied to dye liquor degradation2Catalyst and preparation method thereof - Google Patents
PVP-Si @ TiO applied to dye liquor degradation2Catalyst and preparation method thereof Download PDFInfo
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- CN113262818A CN113262818A CN202110624723.9A CN202110624723A CN113262818A CN 113262818 A CN113262818 A CN 113262818A CN 202110624723 A CN202110624723 A CN 202110624723A CN 113262818 A CN113262818 A CN 113262818A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000006731 degradation reaction Methods 0.000 claims abstract description 27
- 230000015556 catabolic process Effects 0.000 claims abstract description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 239000011941 photocatalyst Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 238000003760 magnetic stirring Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 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 description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- BXDGSXMFTGZLDT-UHFFFAOYSA-N dichloro-bis(2-ethylhexyl)silane Chemical compound CCCCC(CC)C[Si](Cl)(Cl)CC(CC)CCCC BXDGSXMFTGZLDT-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- FGWRMMTYIZKYMA-UHFFFAOYSA-N tert-butyl-hydroxy-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)O FGWRMMTYIZKYMA-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012074 organic phase Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 33
- 239000004408 titanium dioxide Substances 0.000 abstract description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001045 blue dye Substances 0.000 abstract description 9
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 7
- 229940043267 rhodamine b Drugs 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000010865 sewage Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002211 L-ascorbic acid Substances 0.000 description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 240000006413 Prunus persica var. persica Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- -1 azo aromatic amine Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
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- B01J35/39—
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses PVP-Si @ TiO applied to dye liquor degradation2The preparation method of the catalyst comprises the steps of synthesizing PVP-Si nano particles through two-step solvothermal reaction, compounding the PVP-Si nano particles and titanium dioxide, and finally preparing the PVP-Si @ TiO2A composite material. The photocatalyst is used for realizing the efficient degradation of rhodamine B dye solution and methylene blue dye solution.
Description
Technical Field
The invention relates to the technical field of photocatalysis and dye liquor degradation, in particular to PVP-Si @ TiO applied to dye liquor degradation2A catalyst and a preparation method thereof.
Background
In 1972, Fujishima and Honda were in the n-type semiconductor TiO2The electrode shows the reaction of water splitting by photocatalysis, and opens the introduction of new multi-phase photocatalysis, and the research on photocatalytic oxidation of titanium dioxide raises the heat tide. The titanium dioxide photocatalytic oxidation method is a green advanced oxidation technology, and realizes photoelectric conversion and photochemical conversion under the promotion of a titanium dioxide catalyst through the high-efficiency utilization of solar energy. In recent decades, people often apply the photocatalytic oxidation technology of titanium dioxide to the field of sewage treatment. Adding a certain amount of titanium dioxide catalyst into a water pollution system, and then enabling the titanium dioxide to be excited by light to generate electron-hole pairs and dissolved oxygen and water molecules adsorbed on the surface of the catalyst through the radiation effect of lightAnd the generated hydroxyl free radicals and other free radicals with strong oxidizability can degrade and mineralize pollutants. However, the composition of sewage is complex, and many organic pollutants with macromolecular structures are extremely difficult to degrade. Rhodamine B is an artificially synthesized dye with bright peach red color, can be used as a cell fluorescent coloring agent and a metal detection agent in a laboratory, and also relates to the fields of cosmetic washing and protection, hair-scalding and dyeing liquid medicine, paper-making technology, colored glass, fireworks and crackers and the like. Because the rhodamine B dye liquor sewage contains a large amount of azo dyes of azo aromatic amine, the sewage is catalyzed and degraded only by a single titanium dioxide material, the degrading effect is generally limited, and the ideal state is not achieved.
Disclosure of Invention
In order to solve the problems, the invention develops PVP-Si @ TiO2The composite material utilizes PVP-Si nano particles to catalyze and degrade organic sewage in cooperation with titanium dioxide. The invention also provides PVP-Si @ TiO applied to dye liquor degradation2The technical scheme of the catalyst and the preparation method thereof comprises the following steps:
step 1: mixing and stirring the PVP solution and the organic silicon source for 10-30min under magnetic stirring; adding ascorbic acid solution, and adjusting the pH of the mixture solution to 4-6; then heating in water bath under magnetic stirring to obtain a PVP-Si precursor solution;
step 2: transferring the PVP-Si precursor solution prepared in the step 1 into a reaction kettle, and carrying out solvent heat treatment; after the reaction is finished, washing the product for 2-3 times by using absolute ethyl alcohol and deionized water respectively, carrying out centrifugal separation at the rotating speed of 1000rpm/min, and then drying in a 60 ℃ oven to obtain PVP-Si nano particles;
and step 3: mixing the PVP-Si nano particles prepared in the step 2 with absolute ethyl alcohol, and performing ultrasonic dispersion for 10-20 min; then adding tetrabutyl titanate under magnetic stirring, and stirring for 10-20 min; dropwise adding a proper amount of hydrochloric acid solution with the mass fraction of 9% until the titanium source is completely hydrolyzed; stirring for 30min, transferring the mixture into a reaction kettle, and carrying out solvent heat treatment; after the reaction is finished, cleaning the product by deionized waterCentrifuging and drying to obtain PVP-Si @ TiO2A composite material.
Preferably, the technical solution further comprises part or all of the following technical features:
preferably, step 1 is performed by one of bis (2-ethylhexyl) dichlorosilane, tert-butyldimethylmonohydroxysilane, or 3-aminopropyltriethoxysilane.
Preferably, the titanium source in step 1 is one of tetrabutyl titanate, isopropyl titanate, titanium trichloride, titanium tetrachloride and titanium tetrafluoride.
Preferably, the volume ratio of the PVP solution, the organic silicon source and the ascorbic acid solution in the step 1 is 20 (2.5-5) to (2-3).
Preferably, the concentration of the PVP solution in the step 1 is (0.02-0.05) g/mL, and the concentration of the ascorbic acid solution is 0.1 mmol/L.
Preferably, the water bath heating in the step 1 is heating at 65-80 ℃ for 3-6 h.
Preferably, the solvent heat treatment in step 2 is heating at 120-150 ℃ for 5-10 h.
Preferably, the mass-to-volume ratio of the PVP-Si nanoparticles, the tetrabutyl titanate and the hydrochloric acid in the step 3 is (0.05-1) g:10mL (0.2-2) mL.
Preferably, the solvent heat treatment in step 3 is heating at 150-180 ℃ for 12-24 h.
Further, the PVP-Si @ TiO is prepared by the scheme2A composite material.
Further, PVP-Si @ TiO prepared by adopting the scheme2The composite material is used as a photocatalyst and is applied to the field of dye liquor degradation.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention prepares PVP-Si @ TiO2The composite material is compounded by silicon nano particles modified by high molecular organic PVP and titanium dioxide. The PVP-Si nano particles have the characteristics of high molecular polymers, so that the adsorption capacity of the material can be enhanced; when it is composited with titanium dioxide, isThe surface of the titanium dioxide provides more reactive active sites, promotes the transfer effect of electrons and holes between the catalyst and pollutants, further leads the material to have high photocatalytic activity, can effectively degrade rhodamine B dye liquor, can efficiently degrade methylene blue dye liquor, and has excellent performance in the field of dye liquor degradation.
Drawings
Fig. 1 is an XRD pattern of the catalyst prepared in example 1.
FIG. 2 is a graph showing the degradation performance of the catalytic materials prepared in example 1 and comparative examples 1-2 on methylene blue dye liquor.
FIG. 3 is a graph showing the degradation performance of the catalytic materials prepared in example 1 and comparative examples 1-2 on rhodamine B dye solutions.
Detailed Description
To further clarify the disclosure, features and advantages of the present invention, reference will now be made to the following examples and to the accompanying drawings.
Example 1
PVP-Si @ TiO prepared in embodiment 1 of the invention2A composite material comprising the steps of:
step 1: under magnetic stirring, mixing and stirring 20mL of PVP solution with 0.05g/mL and 4mL of 3-aminopropyltriethoxysilane with 0.1mmol/L for 20 min; then adding 2mL of 0.1mol/L ascorbic acid solution, and adjusting the pH value of the mixture solution to 5; then heating in water bath at 70 ℃ for 3h under magnetic stirring to obtain a PVP-Si precursor solution;
step 2: transferring the PVP-Si precursor solution prepared in the step 1 into a reaction kettle, and heating for 6 hours at 120 ℃; after the reaction is finished, respectively cleaning the product for 3 times by using absolute ethyl alcohol and deionized water, carrying out centrifugal separation at the rotating speed of 1000rpm/min, and then drying in a drying oven at 60 ℃ to obtain PVP-Si nano particles;
and step 3: mixing 0.5g of PVP-Si nano particles prepared in the step 2 with 50mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 20 min; then adding 10mL of tetrabutyl titanate under magnetic stirring, and stirring for 15 min; then dropwise adding 2mL of hydrochloric acid solution until the titanium source is completely hydrolyzed; stirring for 30min, mixingTransferring the mixture into a reaction kettle, and heating the mixture for 24 hours at 160 ℃; after the reaction is finished, cleaning the product with deionized water, centrifuging and drying to obtain PVP-Si @ TiO2A composite material.
Example 2
PVP-Si @ TiO prepared in embodiment 2 of the invention2A composite material comprising the steps of:
step 1: under magnetic stirring, mixing and stirring 20mL of PVP solution with 0.03g/mL and 3mL of 3-aminopropyltriethoxysilane with 0.1mmol/L for 20 min; then adding 2mL of 0.1mol/L ascorbic acid solution, and adjusting the pH value of the mixture solution to 5; then heating in water bath at 70 ℃ for 3h under magnetic stirring to obtain a PVP-Si precursor solution;
step 2: transferring the PVP-Si precursor solution prepared in the step 1 into a reaction kettle, and heating for 6 hours at 120 ℃; after the reaction is finished, respectively cleaning the product for 3 times by using absolute ethyl alcohol and deionized water, carrying out centrifugal separation at the rotating speed of 1000rpm/min, and then drying in a drying oven at 60 ℃ to obtain PVP-Si nano particles;
and step 3: mixing 0.3g of PVP-Si nano particles prepared in the step 2 with 50mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 20 min; then adding 10mL of tetrabutyl titanate under magnetic stirring, and stirring for 15 min; then dropwise adding 1mL of hydrochloric acid solution until the titanium source is completely hydrolyzed; stirring for 30min, transferring into a reaction kettle, and heating at 160 deg.C for 24 hr; after the reaction is finished, cleaning the product with deionized water, centrifuging and drying to obtain PVP-Si @ TiO2A composite material.
Example 3
PVP-Si @ TiO prepared in embodiment 3 of the invention2A composite material comprising the steps of:
step 1: under magnetic stirring, mixing and stirring 20mL of PVP solution with 0.03g/mL and 3mL of bis (2-ethylhexyl) dichlorosilane with the concentration of 0.1mmol/L for 20 min; then adding 2mL of 0.1mol/L ascorbic acid solution, and adjusting the pH value of the mixture solution to 5; then heating in water bath at 70 ℃ for 3h under magnetic stirring to obtain a PVP-Si precursor solution;
step 2: transferring the PVP-Si precursor solution prepared in the step 1 into a reaction kettle, and heating for 6 hours at 120 ℃; after the reaction is finished, respectively cleaning the product for 3 times by using absolute ethyl alcohol and deionized water, carrying out centrifugal separation at the rotating speed of 1000rpm/min, and then drying in a drying oven at 60 ℃ to obtain PVP-Si nano particles;
and step 3: mixing 0.1g of PVP-Si nano particles prepared in the step 2 with 50mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 20 min; then adding 10mL of tetrabutyl titanate under magnetic stirring, and stirring for 15 min; then dropwise adding 1mL of hydrochloric acid solution until the titanium source is completely hydrolyzed; stirring for 30min, transferring into a reaction kettle, and heating at 160 deg.C for 24 hr; after the reaction is finished, cleaning the product with deionized water, centrifuging and drying to obtain PVP-Si @ TiO2A composite material.
Comparative example 1
Comparative example 1 of the present invention differs from example 1 in that a titania material was prepared without the addition of PVP-Si nanoparticles.
Comparative example 2
Comparative example 2 of the present invention is different from example 1 in that a PVP-Si nanoparticle was prepared without adding titanium dioxide.
Testing photocatalytic degradation dye liquor:
1. testing parameters:
the invention selects a 300W xenon lamp as a light source; selecting the material prepared by the scheme as a catalyst; selecting rhodamine dye liquor and methylene blue dye liquor as test dye liquor, and unifying the concentration of the dye liquor to be 0.5 x 10-4mol/L; the test distance between the unified dye liquor and a xenon lamp is 12 cm.
2. The testing steps are as follows:
(1) adding 20mg of catalyst into a beaker completely wrapped by tinfoil, adding 100 mL of dye solution into the beaker, ultrasonically dispersing for 5-10min, then placing the beaker on a magnetic stirrer to ensure that the dye solution is fully contacted with the catalyst, at the moment, using a suction tube to draw 1mL of dye solution into a centrifuge tube wrapped by the tinfoil, and recording a sample as L0; after stirring for 30min, using a suction tube to extract 1mL of dye solution into the centrifuge tube wrapped by the tinfoil, and recording the sample as L1;
(2) uncovering the tin foil covered at the upper end of the beaker, turning on a xenon lamp, and irradiating by aiming at the beaker; drawing 1mL of dye solution into a centrifuge tube wrapped by tinfoil by using a pipette every 5min, sequentially recording samples as L2, L3, L4 and … Ln (n is 7), and carrying out a dot taking experiment for 30min in total;
(3) centrifuging the obtained samples respectively, and loading the supernatant into a centrifuge tube completely wrapped by new tinfoil; then deionized water is used as a reference sample, and an ultraviolet spectrophotometer is used for detecting the absorbance of the dye liquor, so that the condition that the degradation of the dye liquor changes along with the time is obtained (the degradation rate is A)Ln/AL1100% of the total weight; wherein A isL1Initial absorbance of the dye liquor for the photodegradation test, ALnAbsorbance of Ln dye solution at the time of photodegradation test).
Through the above experimental detection, the dye liquor degradation curves shown in fig. 2 and fig. 3 can be obtained. Wherein FIG. 2 is a graph showing the degradation profile of the catalysts prepared in example 1 of the present invention and comparative examples 1-2 to methylene blue dye liquor. From FIG. 1, it can be observed that PVP-Si @ TiO2The catalyst has the best effect on degrading the methylene blue dye liquor, can degrade the dye liquor by nearly 90 percent within 20min, and can basically degrade the dye liquor into a colorless transparent state within 25 min; while PVP-Si catalyst and TiO2The catalyst can only degrade methylene blue dye liquor by nearly 70 percent within 30 min. FIG. 3 is a graph showing the degradation curve of the catalysts prepared in example 1 and comparative examples 1-2 of the present invention to rhodamine B dye liquor. From FIG. 3, it can be observed that PVP-Si @ TiO2The catalyst has good degradation effect on rhodamine B dye liquor, can degrade the dye liquor by 87.3 percent within 25min, and can only degrade methylene blue dye liquor by 64.2 percent within 30 min; TiO 22The catalyst can only degrade methylene blue dye liquor by about 70.6 percent within 30 min.
In summary, PVP-Si @ TiO prepared in example 1 of the present invention was compared to comparative examples 1-22The catalyst has higher degradation rate to the two dye solutions, which also indicates that PVP-Si @ TiO2The composite material has high-efficiency effect on dye liquor degradation.
The raw materials listed in the invention, the values of the upper and lower intervals of the raw materials of the invention and the values of the upper and lower intervals of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed here. While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. Such modifications and variations are considered to be within the scope of the invention.
Claims (10)
1. PVP-Si @ TiO applied to dye liquor degradation2The preparation method of the catalyst is characterized by comprising the following steps:
step 1: mixing and stirring the PVP solution and the organic silicon source for 10-30min under magnetic stirring; adding ascorbic acid solution, and adjusting the pH of the mixture solution to 4-6; then heating in water bath under magnetic stirring to obtain a PVP-Si precursor solution;
step 2: transferring the PVP-Si precursor solution prepared in the step 1 into a reaction kettle, and carrying out solvent heat treatment; after the reaction is finished, washing the product for 2-3 times by using absolute ethyl alcohol and deionized water respectively, carrying out centrifugal separation at the rotating speed of 1000rpm/min, and then drying in a 60 ℃ oven to obtain PVP-Si nano particles;
and step 3: mixing the PVP-Si nano particles prepared in the step 2 with absolute ethyl alcohol, and performing ultrasonic dispersion for 10-20 min; then adding a titanium source under magnetic stirring, and stirring for 10-20 min; then dropwise adding a hydrochloric acid solution until the titanium source is completely hydrolyzed; stirring for 30min, transferring the mixture into a reaction kettle, and carrying out solvent heat treatment; after the reaction is finished, cleaning the product with deionized water, centrifuging and drying to obtain PVP-Si @ TiO2A composite material.
2. PVP-Si @ TiO applied to dye liquor degradation according to claim 12The preparation method of the catalyst is characterized in that the organic phase in the step 1The silicon source is one of bis (2-ethylhexyl) dichlorosilane, tert-butyl dimethyl monohydroxysilane or 3-aminopropyltriethoxysilane.
3. PVP-Si @ TiO applied to dye liquor degradation according to claim 12The preparation method of the catalyst is characterized in that the titanium source in the step 1 is one of tetrabutyl titanate, isopropyl titanate, titanium trichloride, titanium tetrachloride or titanium tetrafluoride.
4. PVP-Si @ TiO applied to dye liquor degradation according to claim 12The preparation method of the catalyst is characterized in that the volume ratio of the PVP solution, the 3-aminopropyl triethoxysilane and the ascorbic acid solution in the step 1 is 20 (2.5-5) to (2-3).
5. PVP-Si @ TiO applied to dye liquor degradation according to claim 12The preparation method of the catalyst is characterized in that the concentration of the PVP solution in the step 1 is (0.02-0.05) g/mL, and the concentration of the ascorbic acid solution is 0.1 mmol/L.
6. PVP-Si @ TiO applied to dye liquor degradation according to claim 12The preparation method of the catalyst is characterized in that the water bath heating in the step 1 is heating for 3-6h at 65-80 ℃.
7. PVP-Si @ TiO applied to dye liquor degradation according to claim 12The preparation method of the catalyst is characterized in that the solvent heat treatment in the step 2 is heating for 5-10h at the temperature of 120-150 ℃.
8. PVP-Si @ TiO applied to dye liquor degradation according to claim 12The preparation method of the catalyst is characterized in that the mass-volume ratio of the PVP-Si nano particles, the tetrabutyl titanate and the hydrochloric acid in the step 3 is (0.05-1) g, 10mL (0.2-2) mL.
9. Root of herbaceous plantThe PVP-Si @ TiO composition as claimed in claim 1 for use in dye liquor degradation2The preparation method of the catalyst is characterized in that the solvent heat treatment in the step 3 is heating at 150-180 ℃ for 12-24 h.
10. PVP-Si @ TiO produced by the production method according to any one of claims 1 to 92The composite material is used as a photocatalyst and is applied to the field of dye liquor degradation.
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