CN111282572A - Composite material with near-infrared light catalysis effect and preparation method and application thereof - Google Patents
Composite material with near-infrared light catalysis effect and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 230000000694 effects Effects 0.000 title claims description 12
- 238000006555 catalytic reaction Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title abstract description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 abstract description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 5
- 229940075624 ytterbium oxide Drugs 0.000 claims abstract description 5
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 22
- 230000001699 photocatalysis Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000007146 photocatalysis Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 229910021644 lanthanide ion Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000007861 rambutan Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 244000011919 rambutan Species 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000002256 photodeposition Methods 0.000 abstract description 4
- 229910001961 silver nitrate Inorganic materials 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000009388 chemical precipitation Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 description 18
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 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 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 239000007788 liquid Substances 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 235000005811 Viola adunca Nutrition 0.000 description 2
- 240000009038 Viola odorata Species 0.000 description 2
- 235000013487 Viola odorata Nutrition 0.000 description 2
- 235000002254 Viola papilionacea Nutrition 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000183331 Nephelium lappaceum Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000000628 photoluminescence spectroscopy Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a preparation method of a composite material with a near-infrared light catalytic effect. YF is prepared from yttrium oxide, thulium oxide, ytterbium oxide, ammonium fluoride and the like through a simple hydrothermal method3:Tm3+、Yb3+An up-converting luminescent material; preparing YF from silver nitrate and sodium hydroxide by chemical precipitation3:Tm3+、Yb3+/Ag2An O composite material; YF is prepared by a photo-deposition method3:Tm3+、Yb3+/Ag2O @ Ag composite material. The catalyst prepared by the method has good stability and stable chemical property, and can be repeatedly used. Can be used inThe organic pollutants are degraded under the irradiation of visible light and near infrared light, and the method has important practical value in environmental purification.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a composite material with a near-infrared photocatalytic effect, and a preparation method and application thereof.
Background
The photocatalytic technology can effectively solve the problems of energy and environment, and is receiving increasingly wide attention. The photocatalytic material can not only utilize sunlight for hydrolysis to produce hydrogen, but also decompose harmful substances and wastes generated in production and living, and solve the problems of energy and environment for human survival. At present, the electron-hole pair recombination rate generated after the photocatalyst is irradiated by light is high, the photon utilization efficiency is low, and the photocatalytic activity is not high. It is therefore necessary to investigate the modification of semiconductor photocatalysts, the purpose and effect of which include the suppression of electron-hole pair recombination to improve quantum efficiency.
Solar energy is the most important natural resource for human beings, and provides energy for human beings to maintain normal life directly or indirectly, but the parts of the sunlight, namely ultraviolet light (4%) and near infrared light (50%), are not fully utilized. YF3:Tm3+、Yb3+The up-conversion luminescent material can realize full-spectrum emission of ultraviolet-visible-near infrared (UV-Vis-NIR), and has the advantages of high penetration depth, wide absorption range, high luminous intensity, low toxicity and the like, so that the up-conversion luminescent material has wider application scenes.
Disclosure of Invention
The invention aims to provide a preparation method of a composite photocatalyst, which is simple in preparation method, convenient to operate and high in catalysis efficiency.
In order to achieve the purpose, the invention adopts the technical scheme that:
a composite material with near infrared light catalytic effect is prepared by the following steps:
1) heating and stirring yttrium oxide, thulium oxide and ytterbium oxide in dilute nitric acid until the solution is clear, adjusting the pH value of the solution by using ammonia water after the solution is cooled to room temperature, adding ethylene diamine tetraacetic acid disodium powder and stirring uniformly, adding ammonium fluoride and stirring for 1-2h, then placing the solution in a high-pressure hydrothermal kettle, placing the high-pressure hydrothermal kettle in a drying oven for heating and reacting, cooling the high-pressure hydrothermal kettle to room temperature after the reaction is finished, centrifugally washing the product in the kettle, drying the product in the drying oven, and placing the dried powder in a muffle furnace for calcining to prepare YF3:Tm3+、Yb3+Powder;
2) YF obtained in the step 1)3:Tm3+、Yb3+Stirring the powder in deionized water, adding AgNO3Stirring in water bath at constant temperature, adding sodium hydroxide solution dropwise, stirring for 1-2 hr, cooling to room temperature, centrifuging, washing precipitate, and drying in oven at 50 deg.C to obtain YF3:Tm3+、Yb3+/Ag2And (3) an O composite material.
3) Mixing AgNO3Stirring and dissolving the mixture in deionized water until the mixture is clear, and adding YF obtained in the step 2)3:Tm3+、Yb3+/Ag2Stirring O powder for 1-2h, irradiating the solution under a 300w xenon lamp for 30min for carrying out a light deposition reaction, washing with deionized water after the reaction is finished, and drying in a vacuum oven at 80 ℃ to obtain YF3:Tm3+、Yb3+/Ag2O @ Ag composite material.
Preferably, in the above composite material with near infrared light catalytic effect, in step 1), yttrium oxide, ytterbium oxide, thulium oxide and ammonium fluoride are added in a molar ratio of 0.795:0.2:0.005: 6; and the lanthanide ion, disodium ethylene diamine tetraacetate, is 2: 1.
Preferably, in the above composite material with near infrared photocatalytic effect, in step 1), the PH of the solution is adjusted to 2-3 by ammonia water.
Preferably, in the step 1), the heating temperature is 160-180 ℃, and the reaction time is 40-48 h; the calcining temperature in the muffle furnace is 600-700 ℃, and the calcining time is 1-2 h.
Preferably, the composite material with near infrared photocatalysis effect in the step 2), according to the mass ratio, (YF)3:Tm3+、Yb3+):AgNO3＝1：0.7-3.0。
Preferably, in the step 2), the constant temperature is 60-70 ℃, and the stirring time is 30-45 min.
Preferably, the composite material with near infrared photocatalysis effect in the step 3) is prepared by (YF)3:Tm3+、Yb3+/Ag2O):AgNO3＝1:0.07。
The composite material with the near infrared light catalytic effect is applied to degrading organic pollutants under the irradiation of near infrared light.
Preferably, for the above use, the organic contaminant is rambutan B.
The invention has the beneficial effects that:
1) YF prepared by the invention3:Tm3+、Yb3+The powder has small size, good crystallinity, strong up-conversion luminous intensity and strong blue-violet light displayed by PL spectrum.
2) The invention is in YF3:Tm3+、Yb3+Coated with Ag2After O, the sample is irradiated by near infrared light, and the photocatalytic activity of the sample is analyzed through an experiment of degrading rhodamine B in a liquid phase, and YF is found under the irradiation of the near infrared light3:Tm3+、Yb3+/Ag2The O photocatalyst has certain photocatalytic effect, when being YF3:Tm3+、Yb3+With AgNO3YF when the mass ratio of (1: 1.46) is3:Tm3+、Yb3+/Ag2The degradation rate of the O composite material is highest.
3) The invention is in YF3:Tm3+、Yb3+/Ag2After Ag particles are loaded on the surface of O, the photocatalytic activity is obviously enhanced, and the Ag particles reduce the recombination of photon-generated carriers in the reaction processWhen the Ag particle is supported (AgNO)3Relative to YF3:Tm3+、Yb3+/Ag2O) is 7 wt%, the degradation efficiency of rhodamine B is improved from 24.6% to 63.9%.
4) The catalyst prepared by the method of the invention has lower forbidden bandwidth. The lower forbidden bandwidth reduces the transmission distance of the photo-generated electron holes, improves the separation efficiency of the photo-generated electron holes, reduces the recombination rate, and greatly improves the photocatalytic activity of the photocatalyst under the irradiation of near infrared light. The catalyst prepared by the method has good stability and stable chemical property, and can be repeatedly used.
Drawings
FIG. 1 is a YF prepared in example 13:Tm3+、Yb3+The XRD pattern of the up-converted luminescent material.
FIG. 2 is a YF prepared in example 13:Tm3+、Yb3+SEM images of upconverted luminescent materials.
FIG. 3 is a YF prepared in example 13:Tm3+、Yb3+PL spectrum of the upconverting luminescent material.
FIG. 4 is a YF prepared in example 23:Tm3+、Yb3+/Ag2XRD pattern of O composite.
FIG. 5 is a YF prepared in example 33:Tm3+、Yb3+/Ag2XRD pattern of O @ Ag composite photocatalyst.
FIG. 6 is a series of YF prepared in example 23:Tm3+、Yb3+/Ag2And (3) a rate contrast diagram of liquid phase degradation of rhodamine B of the O composite material under near infrared light irradiation.
FIG. 7 is a series of YF prepared in example 33:Tm3+、Yb3+/Ag2And (3) a comparison graph of the rate of liquid phase degradation of rhodamine B of the O @ Ag composite material under near infrared light irradiation.
Detailed Description
Example 1YF3:Tm3+、Yb3+Up-converting luminescent materials
(I) preparation method
According to preparation 8 mmoleY0.795Yb0.2Tm0.005F3In a ratio of 0.72gY2O3、0.0077gTm2O3And 0.32gYb2O3Adding into 25mL of dilute nitric acid solution with concentration of 3mol/L, heating to 80 deg.C, stirring to obtain clear solution, adjusting pH to 2-3 with dilute ammonia water, adding 1.49g (4mmol) of disodium edetate as surfactant to change sample morphology and size, stirring for 10min, adding 1.02g NH4F, after vigorously stirring for 1h, putting the liquid into a 100ml high-temperature high-pressure reaction kettle, and putting the high-temperature high-pressure reaction kettle into an oven at 180 ℃ for hydrothermal reaction for 48 h. After the high-pressure hydrothermal kettle is cooled to room temperature, the high-pressure hydrothermal kettle is centrifugally washed by deionized water and absolute ethyl alcohol, and finally the high-pressure hydrothermal kettle is dried in an oven at 80 ℃ and roasted in a muffle furnace at 700 ℃ for 1h to obtain YF3:Tm3+、Yb3+Luminescent powder.
(II) detection
FIG. 1 is a pure YF3:Tm3+、Yb3+And (4) XRD detection of the photocatalyst sample. As can be seen from fig. 1, no other peaks were present, indicating that no other impurity phases were present in the product, resulting in a single phase. It can be seen from fig. 1 that the sample has better crystallinity. FIG. 2 is a pure YF3:Tm3+、Yb3+SEM examination of photocatalyst samples. As can be seen in FIG. 2, pure YF3:Tm3+、Yb3+Shows the morphology of irregular melt aggregation, with the diameter of the individual irregular morphology at 100-200 nm. FIG. 3 is a pure YF3:Tm3+、Yb3+PL spectroscopy detection of the photocatalyst sample. As can be seen from fig. 3, the PL spectrum shows intense blue-violet light.
Example 2YF3:Tm3+、Yb3+/Ag2O composite material
(I) preparation method
Three YF portions of example 1 were weighed using a coprecipitation method3:Tm3+、Yb3+Adding 0.1g of powder into three beakers filled with 50ml of deionized water, respectively, performing ultrasonic treatment for 30min, and stirringStirring for 30 min. Then according to YF3:Tm3+、Yb3+With Ag2Adding AgNO with corresponding mass into the mixture with the mass ratio of O being 1:1, 1:2 and 1:4 respectively3Then stirring the mixture in a water bath kettle at the constant temperature of 60 ℃ for 30 min. Then respectively slowly dripping 50ml of 0.2mol/l NaOH solution into the three solutions, stirring in a water bath at 60 ℃ for 1h, naturally cooling to room temperature, collecting precipitates after centrifugation for 5min at 8000r/min, washing with deionized water for 3 times, and then placing in a forced air oven at 50 ℃ for drying overnight to prepare a series of YF3:Tm3+、Yb3+/Ag2And (3) O photocatalyst.
(II) detection
FIG. 4 is a series of YF3:Tm3+、Yb3+/Ag2And (4) XRD detection of the photocatalyst sample. From FIG. 4, sample YF can be seen3:Tm3 +、Yb3+/Ag2O has good crystallinity, contains both YF3:Tm3+、Yb3+Contains Ag2Characteristic diffraction peak of O, and with Ag2Increasing amount of O-coating, YF3:Tm3+、Yb3+The characteristic peak of (a) continuously decreases.
Example 3YF3:Tm3+、Yb3+/Ag2O @ Ag composite material
(I) preparation method
Using a photo-deposition method, a certain amount of silver nitrate (0.0075g, 0.0125g, 0.0175g and 0.0225g, AgNO)3Relative to YF3:Tm3+、Yb3+/Ag 23% by mass, 5%, 7% by mass and 9% by mass of O) was dissolved in 40ml of deionized water to obtain a silver nitrate solution. Weigh four 0.25g portions of YF from example 23:Tm3+、Yb3+/Ag2O(YF3:Tm3+、Yb3+With AgNO3In a mass ratio of 1:1.46) are respectively dispersed in silver nitrate solution and stirred for 1 h. Then irradiating the solution under a 300w xenon lamp for 30min for carrying out a light deposition reaction, after the reaction is finished, washing the solution with deionized water, and drying the solution in a vacuum oven at 80 ℃ for 12h to obtain a series of YF (YF) loaded with different contents of Ag3:Tm3+、Yb3+/Ag2O @ Ag composite photocatalyst.
(II) detection
FIG. 5 is a series of YF3:Tm3+、Yb3+/Ag2And (3) XRD detection of the O @ Ag composite photocatalyst sample. The characteristic peak of each group of composite photocatalyst is obvious, and the composite catalyst can be seen to be successfully prepared. In addition, YF supported on all Ag3:Tm3+、Yb3+/Ag2No diffraction peak related to the simple substance Ag is found in XRD of O sample, which is probably caused by no formation of large Ag particles, and we preliminarily judge that Ag particles are uniformly dispersed in YF only3:Tm3+、Yb3+/Ag2O the surface of the composite photocatalyst.
Example 4YF3:Tm3+、Yb3+/Ag2Application of O @ Ag composite material
YF prepared in example 2 and example 33:Tm3+、Yb3+/Ag2O and YF3:Tm3+、Yb3+/Ag2And (3) carrying out a photocatalyst material performance test on the O @ Ag photocatalyst. The method comprises the following steps: respectively combining YF3:Tm3+、Yb3+/Ag2O and YF3:Tm3+、Yb3+/Ag20.01g of each O @ Ag is placed in a 100ml glass beaker, 30ml of 10mg/L rhodamine B solution is added into each O @ Ag, and the mixture is stirred for 1 hour in a dark room. A976 nm high-power pump light source is used as the only light source for the catalytic test, a circular light spot with the diameter of 1cm is adjusted to be irradiated on the surface of a catalytic system before illumination is started, 3ml of sample liquid is sampled by a centrifuge tube every 2h after the catalysis is started, the sample liquid is centrifuged for 5min by a centrifuge, supernatant liquid is taken in a cuvette by a dropper, the concentration of a fuel solution is determined by uv-3600, and the photocatalytic performance of the composite photocatalyst is determined according to the light absorption condition of residual dye in the solution. As a result, as shown in FIGS. 6 and 7, Ag was observed after 10 hours of light irradiation2O-clad YF3:Tm3+、Yb3+The degradation rate of the sample of the powder to the rhodamine B solution is not high, and when the sample is YF3:Tm3+、Yb3+With AgNO3At a mass ratio of 1:1.46The degradation efficiency is the best, but the degradation rate is only 24.6 percent because of Ag2The forbidden band width of O is narrow, and valence band electrons and conduction band holes are easy to recombine, so that the degradation efficiency is reduced. In YF3:Tm3+、Yb3+/Ag2Sample YF after photo-deposition of Ag particles on O sample3:Tm3+、Yb3+/Ag2The photocatalytic efficiency of O @ Ag (minus 3%, -5%, -7%, and minus 9%) is obviously improved, and the photocatalytic degradation rate is increased and then decreased with the increase of Ag loading, because excessive nano Ag particles are agglomerated, but the specific surface area of the catalyst is lost, and the catalytic activity is reduced. After 7 wt% of Ag particles are subjected to photo-deposition, the degradation efficiency of rhodamine B is improved from 24.6% to 63.9%.
Claims (9)
1. The composite material with near infrared light catalysis effect is characterized by comprising the following steps:
1) heating and stirring yttrium oxide, thulium oxide and ytterbium oxide in dilute nitric acid until the solution is clear, adjusting the pH value of the solution by using ammonia water after the solution is cooled to room temperature, adding ethylene diamine tetraacetic acid disodium powder and stirring uniformly, adding ammonium fluoride and stirring for 1-2h, then placing the solution in a high-pressure hydrothermal kettle, placing the high-pressure hydrothermal kettle in a drying oven for heating and reacting, cooling the high-pressure hydrothermal kettle to room temperature after the reaction is finished, centrifugally washing the product in the kettle, drying the product in the drying oven, and placing the dried powder in a muffle furnace for calcining to prepare YF3:Tm3+、Yb3+Powder;
2) YF obtained in the step 1)3:Tm3+、Yb3+Stirring the powder in deionized water, adding AgNO3Stirring in water bath at constant temperature, adding sodium hydroxide solution dropwise, stirring for 1-2 hr, cooling to room temperature, centrifuging, washing precipitate, and drying in oven at 50 deg.C to obtain YF3:Tm3+、Yb3+/Ag2And (3) an O composite material.
3) Mixing AgNO3Stirring and dissolving the mixture in deionized water until the mixture is clear, and adding YF obtained in the step 2)3:Tm3+、Yb3+/Ag2O powderStirring for 1-2h, irradiating the solution under 300w xenon lamp for 30min for light deposition reaction, washing with deionized water after the reaction is finished, and drying in a vacuum oven at 80 ℃ to obtain YF3:Tm3+、Yb3+/Ag2O @ Ag composite material.
2. The composite material with near infrared photocatalysis effect as claimed in claim 1, wherein: step 1), yttrium oxide, ytterbium oxide, thulium oxide and ammonium fluoride are added according to the molar ratio of 0.795:0.2:0.005: 6; and the lanthanide ion, disodium ethylene diamine tetraacetate, is 2: 1.
3. The composite material with near infrared photocatalysis effect as claimed in claim 1, wherein: in the step 1), the pH value of the solution is adjusted to 2-3 by ammonia water.
4. The composite material with near infrared photocatalysis effect as claimed in claim 1, wherein: in the step 1), the heating temperature is 160-180 ℃, and the reaction time is 40-48 h; the calcining temperature in the muffle furnace is 600-700 ℃, and the calcining time is 1-2 h.
5. The composite material with near infrared photocatalysis effect as claimed in claim 1, wherein: in step 2), (YF) by mass ratio3:Tm3+、Yb3+):AgNO3＝1：0.7-3.0。
6. The composite material with near infrared photocatalysis effect as claimed in claim 1, wherein: in the step 2), the constant temperature is 60-70 ℃, and the stirring time is 30-45 min.
7. The composite material with near infrared photocatalysis effect as claimed in claim 1, wherein: in step 3), (YF) by mass ratio3:Tm3+、Yb3+/Ag2O):AgNO3＝1:0.07。
8. Use of a composite material with near-infrared photocatalytic effect according to claim 1 for degrading organic pollutants under near-infrared irradiation.
9. The use according to claim 8, wherein the organic contaminant is rambutan B.
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