CN110560102B - Bismuth oxyfluoride composite photocatalyst and preparation method and application thereof - Google Patents
Bismuth oxyfluoride composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- IPNGSXQUQIUWKO-UHFFFAOYSA-N bismuth;fluoro hypofluorite Chemical compound [Bi].FOF IPNGSXQUQIUWKO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910016295 BiOF Inorganic materials 0.000 claims abstract description 66
- 239000000243 solution Substances 0.000 claims abstract description 58
- 229910002900 Bi2MoO6 Inorganic materials 0.000 claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 13
- 239000010935 stainless steel Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 139
- 238000003756 stirring Methods 0.000 claims description 34
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 29
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 24
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 14
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [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 claims description 10
- 229940043267 rhodamine b Drugs 0.000 claims description 10
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 5
- 229940075624 ytterbium oxide Drugs 0.000 claims description 5
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 1
- 238000010517 secondary reaction Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 11
- 238000005286 illumination Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- 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
- 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
Abstract
The invention discloses a bismuth oxyfluoride composite photocatalyst and a preparation method and application thereof. With Bi (NO)3)3·5H2O and NH4Using the mixed solution of F as a precursor, and adopting a hydrothermal method to prepare BiOF: Yb3+,Tm3+Powder; mixing BiOF: Yb3+,Tm3+Powder addition to Bi2MoO6The precursor solution is uniformly mixed, then the mixed solution is transferred to a polytetrafluoroethylene stainless steel reaction kettle, placed in an oven for secondary reaction, naturally cooled to room temperature, washed by deionized water and absolute ethyl alcohol for a plurality of times respectively, centrifugally separated, placed in the oven for drying, and Bi is obtained2MoO6/BiOF:Yb3+,Tm3+And (3) powder. The invention has simple synthesis method, low cost, obvious effect of degrading pollutants under visible light and good application prospect in the field of future photocatalysts.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a preparation method and application of a bismuth oxyfluoride composite photocatalyst.
Background
In recent years, environmental pollution is becoming a core topic of people's attention, and it is becoming a current critical task to find a more efficient catalyst for removing pollutants, however, due to the influence of the forbidden bandwidth of a single catalyst, electrons in the valence band cannot be effectively separated from holes in the conduction band, the photocatalytic effect is not ideal, and the photocatalytic field is limited by many factors. The composite photocatalyst can realize effective separation of electrons and holes due to the relative positions of a conduction band and a valence band, so that the recombination of conduction band electrons and valence band holes is inhibited, more active oxidation substances with high oxidation reduction sites can be formed in the process of photocatalytic reaction, organic or inorganic pollutants in the environment can be degraded more quickly through a series of oxidation reduction reactions, the cost is low, the preparation is simple, and the composite photocatalyst has a good application prospect in the future photocatalytic technical field.
Disclosure of Invention
The invention aims to provide the bismuth oxyfluoride composite photocatalyst which is simple in preparation method, convenient to operate, low in cost, mild in condition and high in catalytic efficiency.
The technical scheme adopted by the invention is as follows: the bismuth oxyfluoride composite photocatalyst is Bi2MoO6/BiOF:Yb3+,Tm3+(ii) a Wherein, according to the mass percentage, BiOF is Yb3+,Tm3+Is Bi2 MoO 625% -75%.
Preferably, the bismuth oxyfluoride composite photocatalyst Bi2MoO6/BiOF:Yb3+,Tm3+Medium, Yb3+And Tm3+Respectively in an amount of Bi3+7.5% and 0.5%.
A preparation method of a bismuth oxyfluoride composite photocatalyst comprises the following steps:
1) dissolving ytterbium oxide and thulium oxide in nitric acid, heating and stirring to obtain Yb3+-Tm3+A solution;
2) yb obtained in step 1)3+-Tm3+Dropwise adding the solution into an ethylene glycol solution of bismuth nitrate pentahydrate, uniformly stirring, dropwise adding an ethylene glycol solution of ammonium fluoride, adjusting the pH of the obtained mixed solution by using ammonia water, and stirring at normal temperature to obtain a suspension;
3) transferring the suspension obtained in the step 2) into a stainless steel reaction kettle of polytetrafluoroethylene,after the solvent thermal reaction, natural cooling and filtering are carried out, the obtained precipitate is washed by deionized water and absolute ethyl alcohol, centrifugation and drying are carried out, and BiOF Yb is obtained3+,Tm3+；
4) The BiOF: Yb obtained in the step 3)3+,Tm3+Adding the solution into an ethylene glycol solution of bismuth nitrate pentahydrate, stirring uniformly, dropwise adding the ethylene glycol solution of sodium molybdate dihydrate, and after dropwise adding, adding ethanol under stirring at normal temperature to obtain a suspension;
5) transferring the suspension obtained in the step 4) into a stainless steel reaction kettle made of polytetrafluoroethylene, after hydrothermal reaction, naturally cooling, filtering, washing the obtained precipitate with deionized water and absolute ethyl alcohol, centrifuging, and drying to obtain the bismuth oxyfluoride composite photocatalyst Bi2MoO6/BiOF:Yb3+,Tm3+。
Preferably, in step 2), the pH of the obtained mixed solution is adjusted to 10 by ammonia water, and the mixed solution is stirred for 60min at normal temperature.
Preferably, in the step 3), the temperature of the solvothermal reaction is 160 ℃, and the reaction time is 12 hours; the drying is carried out at 80 ℃ for 24 h.
Preferably, in the step 5), the hydrothermal reaction is carried out at 160 ℃, the reaction time is 12 hours, and the drying temperature is 80 ℃.
The bismuth oxyfluoride composite photocatalyst Bi2MoO6/BiOF:Yb3+,Tm3+The application in degrading organic pollutants under visible light. The method comprises the following steps: adding the bismuth oxyfluoride composite photocatalyst Bi into wastewater containing organic pollutants2MoO6/BiOF:Yb3+,Tm3+And (3) catalytic degradation under visible light.
The invention has the beneficial effects that:
the invention modifies the photocatalysis effect of the BiOF with wider forbidden band width by a two-step solvothermal method, and the obtained bismuth oxyfluoride composite photocatalyst effectively separates conduction band electrons from valence band holes, reduces the recombination efficiency of the electrons and the holes, has higher visible light response effect and better improves the photocatalysis activity. In addition, BiOF is a good light-emitting host, so that Bi2MoO6/BiOF:Yb3+,Tm3+The photocatalyst can realize near infrared photocatalysis under the irradiation of infrared light of 980 nm. The composite photocatalyst has the advantages of simple synthesis method, low cost and obvious pollutant degradation effect under visible light, and has higher photocatalytic activity compared with a single catalyst.
Drawings
Figure 1 is an XRD pattern of different catalysts.
FIG. 2 is an SEM image of various catalysts;
wherein, a is BiOF; b is Bi2MoO6；c:Bi2MoO6/BiOF:Yb3+,Tm3+-50％。
FIG. 3 shows different Bi2MoO6/BiOF:Yb3+,Tm3+A comparison graph of 10mg/L rhodamine B degraded by the composite photocatalyst under visible light (lambda is more than or equal to 400 nm).
FIG. 4 shows Bi2MoO6/BiOF:Yb3+,Tm3+An ultraviolet-visible absorption spectrogram of 10mg/L rhodamine B degraded by the 50% composite photocatalyst under 980 nm.
FIG. 5 shows Bi2MoO6/BiOF:Yb3+,Tm3+-near infrared degradation diagram of 50% composite photocatalyst.
Detailed Description
Example 1 bismuth oxyfluoride composite photocatalyst Bi2MoO6/BiOF:Yb3+,Tm3+
(mono) bismuth oxyfluoride composite photocatalyst Bi2MoO6/BiOF:Yb3+,Tm3+-25％
The preparation method comprises the following steps:
1) 0.0591g of ytterbium oxide and 0.0039g of thulium oxide are dissolved in 10mL of dilute nitric acid with the concentration of 5mol/L, heated, stirred and dissolved to obtain Yb3+-Tm3+And (3) solution.
2) 1.94g of bismuth nitrate pentahydrate is weighed, heated, stirred and dissolved in 40mL of glycol to obtain the glycol solution of the bismuth nitrate pentahydrate. 0.3186g of ammonium fluoride is weighed and dissolved in 20mL of ethylene glycol with stirring to obtain an ethylene glycol solution of ammonium fluoride.
Yb obtained in step 1)3+-Tm3+Dropwise adding the solution into an ethylene glycol solution of bismuth nitrate pentahydrate, stirring at normal temperature for 10min, dropwise adding an ethylene glycol solution of ammonium fluoride, adjusting the pH of the obtained mixed solution to 10 by using ammonia water, and stirring at normal temperature for 1h to obtain a suspension.
3) Transferring the suspension obtained in the step 2) into a stainless steel reaction kettle made of polytetrafluoroethylene, and reacting for 12 hours at 160 ℃. Naturally cooling to room temperature, filtering, centrifugally washing the obtained precipitate with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 80 ℃ for 24 hours to obtain BiOF: Yb3+,Tm3+And (3) powder.
4) 0.97g of bismuth nitrate pentahydrate is weighed, heated, stirred and dissolved in 20mL of glycol to obtain the glycol solution of the bismuth nitrate pentahydrate. 0.242g of sodium molybdate dihydrate is weighed and dissolved in 20mL of glycol by stirring to obtain the glycol solution of the sodium molybdate dihydrate.
Taking 0.1525g BiOF Yb3+,Tm3+The powder is stirred for 1h at normal temperature in ethylene glycol solution of bismuth nitrate pentahydrate to obtain white suspension. And then dropwise adding a glycol solution of sodium molybdate dihydrate, stirring at normal temperature for 1h after dropwise adding, then adding 20mL of ethanol, and continuously stirring for 10min to obtain a suspension.
5) Transferring the suspension obtained in the step 4) into a stainless steel reaction kettle made of polytetrafluoroethylene, reacting for 12 hours at 160 ℃, naturally cooling to room temperature, centrifugally washing the obtained precipitate for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying for 24 hours at 80 ℃ to obtain the bismuth oxyfluoride composite photocatalyst, which is recorded as Bi2MoO6/BiOF:Yb3+,Tm3+-25％。
Bismuth (di) fluoroxide composite photocatalyst Bi2MoO6/BiOF:Yb3+,Tm3+-50％
The preparation method comprises the following steps:
1) 0.0591g of ytterbium oxide and 0.0039g of thulium oxide are dissolved in 10mL of dilute nitric acid with the concentration of 5mol/L, heated, stirred and dissolved to obtain Yb3+-Tm3+And (3) solution.
2) 1.94g of bismuth nitrate pentahydrate is weighed, heated, stirred and dissolved in 40mL of glycol to obtain the glycol solution of the bismuth nitrate pentahydrate. 0.3186g of ammonium fluoride is weighed and dissolved in 20mL of ethylene glycol with stirring to obtain an ethylene glycol solution of ammonium fluoride.
Yb obtained in step 1)3+-Tm3+Dropwise adding the solution into an ethylene glycol solution of bismuth nitrate pentahydrate, stirring at normal temperature for 10min, dropwise adding an ethylene glycol solution of ammonium fluoride, adjusting the pH of the obtained mixed solution to 10 by using ammonia water, and stirring at normal temperature for 1h to obtain a suspension.
3) Transferring the suspension obtained in the step 2) into a stainless steel reaction kettle made of polytetrafluoroethylene, and reacting for 12 hours at 160 ℃. Naturally cooling to room temperature, filtering, centrifugally washing the obtained precipitate with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 80 ℃ for 24 hours to obtain BiOF: Yb3+,Tm3+And (3) powder.
4) 0.97g of bismuth nitrate pentahydrate is weighed, heated, stirred and dissolved in 20mL of glycol to obtain the glycol solution of the bismuth nitrate pentahydrate. 0.242g of sodium molybdate dihydrate is weighed and dissolved in 20mL of glycol by stirring to obtain the glycol solution of the sodium molybdate dihydrate.
Taking 0.305gBiOF Yb3+,Tm3+The powder is stirred for 1h at normal temperature in ethylene glycol solution of bismuth nitrate pentahydrate to obtain white suspension. And then dropwise adding a glycol solution of sodium molybdate dihydrate, stirring at normal temperature for 1h after dropwise adding, then adding 20mL of ethanol, and continuously stirring for 10min to obtain a suspension.
5) Transferring the suspension obtained in the step 4) into a stainless steel reaction kettle made of polytetrafluoroethylene, reacting for 12 hours at 160 ℃, naturally cooling to room temperature, centrifugally washing the obtained precipitate for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying for 24 hours at 80 ℃ to obtain the bismuth oxyfluoride composite photocatalyst, which is recorded as Bi2MoO6/BiOF:Yb3+,Tm3+-50％。
(tri) bismuth oxyfluoride composite photocatalyst Bi2MoO6/BiOF:Yb3+,Tm3+-75％
The preparation method comprises the following steps:
1) 0.0591g of ytterbium oxide and 0.0039g of thulium oxide are dissolved in 10mL of dilute nitric acid with the concentration of 5mol/L, heated, stirred and dissolved to obtain Yb3+-Tm3+And (3) solution.
2) 1.94g of bismuth nitrate pentahydrate is weighed, heated, stirred and dissolved in 40mL of glycol to obtain the glycol solution of the bismuth nitrate pentahydrate. 0.3186g of ammonium fluoride is weighed and dissolved in 20mL of ethylene glycol with stirring to obtain an ethylene glycol solution of ammonium fluoride.
Yb obtained in step 1)3+-Tm3+Dropwise adding the solution into an ethylene glycol solution of bismuth nitrate pentahydrate, stirring at normal temperature for 10min, dropwise adding an ethylene glycol solution of ammonium fluoride, adjusting the pH of the obtained mixed solution to 10 by using ammonia water, and stirring at normal temperature for 1h to obtain a suspension.
3) Transferring the suspension obtained in the step 2) into a stainless steel reaction kettle made of polytetrafluoroethylene, and reacting for 12 hours at 160 ℃. Naturally cooling to room temperature, filtering, centrifugally washing the obtained precipitate with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 80 ℃ for 24 hours to obtain BiOF: Yb3+,Tm3+And (3) powder.
4) 0.97g of bismuth nitrate pentahydrate is weighed, heated, stirred and dissolved in 20mL of glycol to obtain the glycol solution of the bismuth nitrate pentahydrate. 0.242g of sodium molybdate dihydrate is weighed and dissolved in 20mL of glycol by stirring to obtain the glycol solution of the sodium molybdate dihydrate.
Taking 0.4575gBiOF as Yb3+,Tm3+The powder is stirred for 1h at normal temperature in ethylene glycol solution of bismuth nitrate pentahydrate to obtain white suspension. And then dropwise adding a glycol solution of sodium molybdate dihydrate, stirring at normal temperature for 1h after dropwise adding, then adding 20mL of ethanol, and continuously stirring for 10min to obtain a suspension.
5) Transferring the suspension obtained in the step 4) into a stainless steel reaction kettle made of polytetrafluoroethylene, reacting for 12 hours at 160 ℃, naturally cooling to room temperature, centrifugally washing the obtained precipitate for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying for 24 hours at 80 ℃ to obtain the bismuth oxyfluoride composite photocatalyst, which is recorded as Bi2MoO6/BiOF:Yb3+,Tm3+-75％。
(IV) comparative example 1 pure BiOF photocatalyst
The preparation method comprises the following steps:
1.94g of bismuth nitrate pentahydrate is weighed, heated, stirred and dissolved in 40mL of glycol to obtain the glycol solution of the bismuth nitrate pentahydrate. 0.3186g of ammonium fluoride is weighed and dissolved in 20mL of ethylene glycol with stirring to obtain an ethylene glycol solution of ammonium fluoride.
Adding an ethylene glycol solution of ammonium fluoride into an ethylene glycol solution of bismuth nitrate pentahydrate dropwise, stirring for 1h, adjusting the pH of the obtained mixed solution to 10 by using ammonia water, transferring the obtained suspension into a stainless steel reaction kettle of polytetrafluoroethylene, and reacting for 12h at 160 ℃. Naturally cooling to room temperature, filtering, centrifugally washing the obtained precipitate with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 80 ℃ for 24 hours to obtain the pure BiOF photocatalyst.
(V) comparative example 2-pure Bi2MoO6Photocatalyst and process for producing the same
The preparation method comprises the following steps:
0.97g of bismuth nitrate pentahydrate is weighed, heated, stirred and dissolved in 20mL of glycol to obtain the glycol solution of the bismuth nitrate pentahydrate. 0.242g of sodium molybdate dihydrate is weighed and dissolved in 20mL of glycol by stirring to obtain the glycol solution of the sodium molybdate dihydrate.
Dropwise adding the ethylene glycol solution of sodium molybdate dihydrate into the ethylene glycol solution of bismuth nitrate pentahydrate, stirring for 1h, then adding 20mL of ethanol, continuously stirring for 10min, transferring the obtained mixed solution into a stainless steel reaction kettle of polytetrafluoroethylene, and reacting for 12h at 160 ℃. Naturally cooling to room temperature, filtering, centrifugally washing the obtained precipitate for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying at 80 ℃ for 24 hours to obtain pure Bi2MoO6A photocatalyst.
(VI) detection
Figure 1 is an XRD pattern of different catalysts. As can be seen from e in FIG. 1, the XRD of the pure BiOF photocatalyst sample has no other miscellaneous peaks, and is completely consistent with that of the standard card (JCPDS 73-1595), and it can be seen that the pure BiOF photocatalyst sample has better crystallinity. As can be seen from a in FIG. 1, pure Bi2MoO6No other impurity peaks exist in XRD of the photocatalyst sample, which indicates that no other impurity phases exist in the product, and the pure Bi can be seen in full accordance with the standard card (JCPDS 84-0787)2MoO6The sample had better crystallinity. As can be seen from b in FIG. 1, Bi2MoO6/BiOF:Yb3+,Tm3+XRD of 25% composite photocatalyst contains both diffraction peaks of BiOF and Bi2MoO6And is represented by Bi2MoO6Shows that Bi is mainly the diffraction peak of (A) and no other miscellaneous peak is found2MoO6/BiOF:Yb3+,Tm3+The crystallinity of the-25% sample was good. As can be seen from c in FIG. 1, Bi2MoO6/BiOF:Yb3+,Tm3+XRD of 50% composite photocatalyst contains both diffraction peaks of BiOF and Bi2MoO6No other hetero peak was found, indicating that Bi2MoO6/BiOF:Yb3+,Tm3+The crystallinity of the-50% sample was good. As can be seen from d in FIG. 1, Bi2MoO6/BiOF:Yb3+,Tm3+XRD of 75% composite photocatalyst contains both diffraction peaks of BiOF and Bi2MoO6The diffraction peak of (2) and the diffraction peak of BiOF are dominant, and no other miscellaneous peak is found, indicating that Bi is2MoO6/BiOF:Yb3+,Tm3+The crystallinity of the-75% sample was good.
Fig. 2 is an SEM image of different catalysts. Fig. 2 (a) is an SEM of a pure BiOF photocatalyst sample, and it can be seen that the pure BiOF shows a lamellar structure and has a smooth surface. In FIG. 2, (b) is pure Bi2MoO6SEM of photocatalyst sample, visible, pure Bi2MoO6Has a spherical structure, has a rough surface and has a diameter of about 1 micron. In FIG. 2, (c) is Bi2MoO6/BiOF:Yb3 +,Tm3+SEM of 50% photocatalyst sample, visible, Bi2MoO6/BiOF:Yb3+,Tm 3+50% of the lamellar structure is rough, indicating BiOF and Bi2MoO6A complex is formed.
Example 2 bismuth oxyfluoride composite photocatalyst Bi2MoO6/BiOF:Yb3+,Tm3+Application of
(I) Bi2MoO6/BiOF:Yb3+,Tm3+Photocatalytic performance test of composite photocatalyst
The method comprises the following steps: a 300w xenon lamp (lambda is more than or equal to 400nm) is used as a light source, 0.05g of catalyst is added into a 100mL beaker, 50mL (10mg/L) of rhodamine B dye solution is added, and the catalyst system is stirred for 30min in a dark room environment before being illuminated by light, so that the catalyst and the dye reach adsorption-desorption balance; adjusting the light intensity center to irradiate the surface of the catalytic system, taking 3mL every 10min after illumination, centrifuging for 5min at 8000rpm, taking supernatant, measuring the concentration of the residual dye in the solution by uv-3600, and evaluating the catalytic performance of the sample according to the absorbance of the solution.
FIG. 3 shows the effect of different catalysts on degradation of rhodamine B under irradiation of visible light, and from FIG. 3, Bi is shown2MoO6/BiOF:Yb3+,Tm3+The degradation effect of-50% is best, after the illumination is carried out for 30min, the degradation rate of rhodamine B reaches 51.7%, and after the illumination is carried out for 50min, the degradation rate of rhodamine B reaches 99.3%.
(II) Bi2MoO6/BiOF:Yb3+,Tm3+Infrared photocatalysis application of-50% composite photocatalyst
Adding Bi2MoO6/BiOF:Yb3+,Tm3+And (4) carrying out near infrared photocatalyst material performance test on the 50 percent composite photocatalyst.
The method comprises the following steps: using 980nm laser as a light source, adding 0.1g of catalyst into a 50mL beaker, adding 30mL (10mg/L) of rhodamine B dye solution, and stirring for 1h in a dark environment before the illumination of a catalytic system to ensure that the catalyst and the dye reach adsorption-desorption balance; adjusting a circular light spot with the diameter of 1cm to irradiate the surface of the catalytic system, sampling 3ml every 1h after illumination, centrifuging for 5min at 8000rpm, taking supernatant, measuring the concentration of the residual dye in the solution by uv-3600, and evaluating the catalytic performance of the sample according to the absorbance of the solution.
As a result, as shown in FIG. 4, the characteristic peak of the absorption of rhodamine B gradually decreased with the lapse of time under 980nm light irradiation, indicating that the molecular structure of rhodamine B was destroyed, and it was found that Bi2MoO6/BiOF:Yb3+,Tm 3+50% has near infrared photocatalytic effect.
FIG. 5 shows Bi2MoO6/BiOF:Yb3+,Tm3+FIG. 5 shows the near-infrared photocatalytic degradation of 50% under 980nm light compared to a single catalyst, showing that Bi2MoO6/BiOF:Yb3+,Tm3+The near infrared light catalytic effect of-50% is the best, the catalytic effect is compared with Bi2MoO6And BiOF Yb3+,Tm3+The-50% improvement is nearly 45%.
Claims (9)
1. The bismuth oxyfluoride composite photocatalyst is characterized by being Bi2MoO6/BiOF:Yb3+,Tm3+(ii) a Wherein, according to the mass percentage, BiOF is Yb3+,Tm3+Is Bi2MoO625% -75%.
2. The bismuth oxyfluoride composite photocatalyst according to claim 1, wherein the bismuth oxyfluoride composite photocatalyst Bi2MoO6/BiOF:Yb3+,Tm3+Medium, Yb3+And Tm3+Respectively in an amount of Bi3+7.5% and 0.5%.
3. A preparation method of a bismuth oxyfluoride composite photocatalyst is characterized by comprising the following steps:
1) dissolving ytterbium oxide and thulium oxide in nitric acid, heating and stirring to obtain Yb3+-Tm3+A solution;
2) yb obtained in step 1)3+-Tm3+Dropwise adding the solution into an ethylene glycol solution of bismuth nitrate pentahydrate, uniformly stirring, dropwise adding an ethylene glycol solution of ammonium fluoride, adjusting the pH value of the obtained mixed solution by using ammonia water, and stirring at normal temperature to obtain a suspension;
3) transferring the suspension obtained in the step 2) into a stainless steel reaction kettle made of polytetrafluoroethylene, naturally cooling and filtering after the solvent thermal reaction, washing the obtained precipitate with deionized water and absolute ethyl alcohol, centrifuging and drying to obtain BiOF: Yb3+,Tm3+；
4) The BiOF: Yb obtained in the step 3)3+,Tm3+Adding into glycol solution of bismuth nitrate pentahydrate, stirring, dropwise adding glycol solution of sodium molybdate dihydrate, and stirring at room temperatureAdding ethanol to obtain suspension;
5) transferring the suspension obtained in the step 4) into a stainless steel reaction kettle made of polytetrafluoroethylene, after hydrothermal reaction, naturally cooling, filtering, washing the obtained precipitate with deionized water and absolute ethyl alcohol, centrifuging, and drying to obtain the bismuth oxyfluoride composite photocatalyst Bi2MoO6/BiOF:Yb3+,Tm3+。
4. The method according to claim 3, wherein in the step 2), the pH of the mixed solution is adjusted to 10 with ammonia water, and the mixed solution is stirred at room temperature for 60 min.
5. The preparation method according to claim 3, wherein in the step 3), the temperature of the solvothermal reaction is 160 ℃, and the reaction time is 12 h; the drying is carried out at 80 ℃ for 24 h.
6. The preparation method according to claim 3, wherein in the step 5), the hydrothermal reaction is carried out at 160 ℃, the reaction time is 12 hours, and the drying temperature is 80 ℃.
7. The bismuth oxyfluoride composite photocatalyst Bi according to claim 1 or 22MoO6/BiOF:Yb3+,Tm3+The application in degrading organic pollutants under visible light.
8. Use according to claim 7, characterized in that the method is as follows: adding the bismuth oxyfluoride composite photocatalyst Bi described in claim 1 or 2 to wastewater containing organic pollutants2MoO6/BiOF:Yb3+,Tm3+And (3) catalytic degradation under visible light.
9. Use according to claim 7, wherein the organic contaminant is rhodamine B.
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