CN114452987A - PVDF (polyvinylidene fluoride) modified metal oxide catalyst as well as preparation method and application thereof - Google Patents
PVDF (polyvinylidene fluoride) modified metal oxide catalyst as well as preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 48
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 45
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 45
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 9
- 230000000593 degrading effect Effects 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 3
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004098 Tetracycline Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229960001699 ofloxacin Drugs 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 229960002180 tetracycline Drugs 0.000 claims description 2
- 229930101283 tetracycline Natural products 0.000 claims description 2
- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 3
- 230000033558 biomineral tissue development Effects 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- -1 hydroxyl ions Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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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
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2101/345—Phenols
-
- 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
Abstract
The invention provides a PVDF (polyvinylidene fluoride) modified metal oxide catalyst as well as a preparation method and application thereof. The PVDF modified metal oxide catalyst is prepared by uniformly mixing metal oxide powder and PVDF powder and then calcining. The PVDF modified metal oxide catalyst provided by the invention takes PVDF as a modifier, the PVDF modified metal oxide catalyst is prepared by a direct calcination method, the electron cloud density on metal is reduced by introducing fluorine, the Lewis acidity of active metal is enhanced, the decomposition of ozone is promoted to generate more hydroxyl free radicals, the utilization efficiency of the hydroxyl free radicals is improved by adjusting the content of the PVDF, the oxidative degradation of organic pollutants in water is enhanced, and the mineralization degree of the organic pollutants is obviously improved.
Description
Technical Field
The invention belongs to the technical field of water pollution strengthening treatment, and particularly relates to a PVDF modified metal oxide catalyst, and a preparation method and application thereof.
Background
With the continuous and stable growth of economy, the industrial production scale is gradually enlarged, a large amount of industrial wastewater which is high in toxicity and difficult to treat is generated, and serious threats are caused to the quality of a water environment and the health of residents. The catalytic ozonation technology is an efficient and green advanced oxidation technology (AOPs), and can be used for efficiently degrading organic pollutants and is more and more widely applied to the treatment of organic wastewater, particularly refractory organic wastewater. The method and the means for improving the ozone efficiency and enhancing the ozone oxidation capacity by seeking a green, economical, efficient and environment-friendly catalyst become an effective improvement method and means.
The heterogeneous catalysis ozone oxidation efficiency is high, and the solid catalyst can be recycled, so that secondary pollution caused by the catalyst is avoided or weakened, and the use cost of the catalyst is also reduced. In general, the hydroxyl groups and bonded hydroxyl ions on the catalyst surface can accelerate the decomposition of ozone, leading to the formation of hydroxyl radicals or surface complexes followed by intramolecular electron transfer, thereby promoting the degradation of the contaminants. The metal oxide, the supported metal oxide and some novel materials such as activated carbon are used more at present to enhance the catalysis of ozone. The metal oxide can catalyze the decomposition and conversion of ozone into active oxygen species with higher oxidation capacity, and the capacity of the ozone to oxidize and degrade organic pollutants is enhanced. However, the metal oxide catalyst in the prior art has low activity and poor stability, and is not beneficial to large-scale application.
Therefore, the development of a metal oxide catalyst with high catalytic activity, good stability, simple preparation method and low production cost to meet the application requirements of ozone oxidation catalysis is a problem to be solved in the field.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a PVDF modified metal oxide catalyst, and a preparation method and application thereof. The preparation method has simple process and low cost, and is easy for industrial production. The prepared PVDF modified metal oxide catalyst is applied to the catalytic oxidative decomposition of organic pollutants in wastewater by ozone, can enhance the Lewis acidity of metal oxide, promote the decomposition of ozone to generate more hydroxyl free radicals, improve the utilization efficiency of the hydroxyl free radicals by adjusting the content of PVDF, and enhance the oxidative degradation of the organic pollutants in water.
A preparation method of a PVDF modified metal oxide catalyst comprises the following steps: and uniformly mixing metal oxide powder and PVDF powder, and calcining to obtain the PVDF modified metal oxide catalyst.
The preparation method has simple process, introduces fluorine into the metal oxide by adopting a direct calcination mode, reduces the electron cloud density of the metal oxide, promotes the ozone decomposition to generate more hydroxyl free radicals by enhancing the Lewis acidity of the active metal, and effectively enhances the oxidative degradation of organic pollutants in water.
Preferably, the mass ratio of the metal oxide to the PVDF is 1: (0.1 to 20). More preferably 1: (0.1-15). Still more preferably 1: (0.1-5). More preferably 1: (0.5 to 3).
Preferably, the metal oxide is one or more of aluminum oxide, cerium oxide, titanium oxide and manganese oxide. More preferably, alumina or titanium oxide. More preferably alumina.
Preferably, the calcination temperature is 100 to 700 ℃. Further preferably 300 to 700 ℃. More preferably 400 to 600 ℃.
Preferably, the calcination time is 2-48 h. Further preferably 2 to 24 hours. More preferably 5 to 12 hours.
Preferably, after the calcination reaction is finished, washing and drying the calcined product by using ethanol and deionized water to obtain the PVDF modified metal oxide catalyst.
Preferably, the calcination may be performed in a muffle furnace, and the PVDF-modified metal oxide catalyst may be obtained by calcining at a predetermined temperature for a predetermined time, washing, and drying.
A PVDF-modified metal oxide catalyst prepared by any one of the above preparation methods.
The adoption of the catalyst can improve the catalytic activity of the ozone degradation reaction O3The capability of effectively decomposing the water into hydroxyl free radicals can improve the efficiency of degrading and mineralizing organic pollutants in water by ozone reaction, and can be applied to the field of water pollution strengthening treatment.
An application of the PVDF modified metal oxide catalyst in degrading organic pollutants in wastewater.
Application of the catalyst of the present invention to ozone (O)3) In the application of oxidizing and degrading the organic pollutants in the wastewater, the oxidizing and degrading can be effectively enhanced, the mineralization degree of the organic pollutants is improved, and the treatment effect of the organic pollutants in the wastewater is improved.
Preferably, the organic contaminant is one or more of salicylic acid, p-nitrophenol, ofloxacin, tetracycline or an analogue of any of the above compounds. More preferably, p-nitrophenol is used.
Preferably, the PVDF modified metal oxide catalyst is added into wastewater containing organic pollutants, and ozone is introduced to perform catalytic oxidation by ozone.
Preferably, the concentration of the organic pollutants is 10-300 ppm. More preferably 10 to 200 ppm. More preferably 10 to 100 ppm.
Preferably, the input amount of the PVDF modified metal oxide catalyst is 0.1-20 g L-1. More preferably 0.1 to 5g L-1. More preferably 0.1 to 1g L-1。
Preferably, the concentration of the ozone is 0.001 to 1g L-1The flow rate is 10-300 mL min-1. Further preferably, the concentration of the ozone is 0.001 to 0.1g L-1The flow rate is 10-200 mL min-1. Further preferably, the concentration of the ozone is 0.001-0.05 g L-1The flow rate is 40-150 mL min-1。
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the invention takes PVDF as a modifier, adopts a direct calcination method to prepare the PVDF modified metal oxide ozone catalyst, and introduces fluorine into the metal oxide to enhance the Lewis acidity of active metal and promote the decomposition of ozone to generate more hydroxyl radicals; meanwhile, the utilization efficiency of hydroxyl free radicals is improved by adjusting the content of PVDF, the oxidative degradation of organic pollutants in water is enhanced, and the mineralization degree of the organic pollutants is obviously improved.
Drawings
FIG. 1 is an SEM topography of a PVDF-modified alumina catalyst prepared in example 1;
FIG. 2 is a graph showing the time-dependent change of the residual rate of ozone oxidation of p-nitrophenol in the PVDF-modified alumina catalyst prepared in example 1.
Detailed Description
The technical solution of the present invention will be further illustrated by the following examples.
Example 1
The preparation method of the PVDF modified alumina catalyst comprises the steps of uniformly mixing alumina powder and PVDF powder, calcining, and carrying out post-treatment to obtain the PVDF modified metal oxide catalyst.
The method comprises the following specific steps:
a preparation method of a PVDF modified alumina catalyst comprises the following steps:
and 2g of alumina and 2g of PVDF powder are uniformly mixed, the mixture is placed in a crucible to react for 6 hours at 500 ℃ in a muffle furnace, and the obtained solid is washed and dried by ethanol and deionized water and then is dried at low temperature to obtain the PVDF modified alumina catalyst.
The SEM topography of the prepared PVDF modified alumina catalyst is shown in figure 1, and the prepared PVDF modified alumina catalyst is of a layered structure.
Test for degradation Properties
10mg L in 300mL-1Putting a p-nitrophenol solution (water as solvent) in a beaker into a heat collection type magnetic stirrer, and adjusting the temperature of the heat collection type magnetic stirrer to be 25 ℃ and the rotating speed to be 200rpm min-1. Accurately weighing 120mg of the PVDF modified alumina catalyst, adding the PVDF modified alumina catalyst into the p-nitrophenol solution, and introducing O into the system3(concentration 4mg L)-1Flow rate of 120mL min-1) Triggering the ozonization reaction. 5mL (0min, 5min, 10min, 15min, 20min, 25min, 30min) was sampled at 5min intervals, filtered through a 0.22 μm needle filter, and the residual ozone and reactive oxygen species in the filtrate were rapidly quenched with 10 μ L of t-butanol. Each set of experiments was repeated three times.
The method adopts an Agilent 1260 type high performance liquid chromatograph to measure the concentration of the p-nitrophenol, and the analysis conditions are as follows: an Agilent ZORBAX Eclipse XDB-C18 chromatographic column (3.5 μm,4.6x 150mm) is used as a stationary phase, the column temperature is 30 ℃, the mobile phase is a mixed solution of water and methanol (30/70), and the flow rate and the sample introduction amount are respectively 0.8mL min-1And 20. mu.L. The retention time of p-nitrophenol was 2.14 min.
The sample concentration C is measured at 0min, 5min, 10min, 15min, 20min, 25min, and 30mintWith initial concentration C of p-nitrophenol solution0The ratio is ordinate, the time point is abscissa, the graph of the change of the residual rate of p-nitrophenol is plotted, and the result is shown in FIG. 2. As can be seen from FIG. 2, after 30min of reaction, the PVDF-modified alumina catalyst (shown as F-Al in the figure) prepared as described above2O3+O3) The degradation rate of p-nitrophenol solution was 97.8%.
Example 2
A preparation method of a PVDF modified alumina catalyst comprises the following steps:
1g of alumina and 2g of PVDF powder are uniformly mixed, put into a crucible to react for 6 hours at 500 ℃ in a muffle furnace, and the obtained solid is washed and dried by ethanol and deionized water and then dried at low temperature to obtain the PVDF modified alumina catalyst.
After 30min of reaction, the degradation rate of the PVDF-modified alumina catalyst prepared in this example to the paranitrophenol solution was 92.95% by using the degradation performance test method in example 1.
Example 3
A preparation method of a PVDF modified titanium oxide catalyst comprises the following steps:
1g of titanium oxide and 1g of PVDF powder are uniformly mixed, the mixture is placed in a crucible to react for 6 hours at 500 ℃ in a muffle furnace, and the obtained solid is washed and dried by ethanol and deionized water and then dried at low temperature to obtain the PVDF modified titanium oxide as the efficient ozone catalyst.
After 30min of reaction, the degradation rate of the PVDF-modified titanium oxide catalyst prepared in this example to the paranitrophenol solution was 95.2% by using the degradation performance test method in example 1.
Claims (8)
1. The PVDF modified metal oxide catalyst is characterized by being prepared by uniformly mixing metal oxide powder and PVDF powder and then calcining.
2. The PVDF-modified metal oxide catalyst as claimed in claim 1, wherein the mass ratio of the metal oxide to PVDF is 1: (0.1 to 20).
3. The PVDF-modified metal oxide catalyst of claim 1, wherein the metal oxide is one or more of alumina, ceria, titania, and manganese oxide.
4. The PVDF-modified metal oxide catalyst as claimed in claim 1, wherein the calcination temperature is 100-700 ℃ and the calcination time is 2-48 h.
5. A method for preparing the PVDF-modified metal oxide catalyst as defined in any one of claims 1 to 4, comprising:
and uniformly mixing metal oxide powder and PVDF powder, and calcining to obtain the PVDF modified metal oxide catalyst.
6. The application of the PVDF modified metal oxide catalyst as defined in any one of claims 1-4 in degrading organic pollutants in wastewater.
7. The use of claim 6, wherein the organic contaminant is one or more of salicylic acid, p-nitrophenol, ofloxacin, tetracycline or an analogue of any of the above compounds.
8. The use according to claim 6, characterized in that the PVDF modified metal oxide catalyst is added to the wastewater containing organic pollutants, and ozone is introduced; wherein the concentration of the organic pollutants is 10-300 ppm; the input amount of the PVDF modified metal oxide catalyst is 0.1-20 g L-1(ii) a The concentration of the introduced ozone is 0.001-1 g L-1The flow rate is 10-300 mL min-1。
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| K.T. CHEN ET AL.: "Comparison of photodegradative efficiencies and mechanisms of Victoria Blue R assisted by Nafion-coated and fluorinated TiO2 photocatalysts", 《JOURNAL OF HAZARDOUS MATERIALS》, pages 598 * |
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