CN107008336B - photocatalytic materials SnO2@Fe2O3Preparation and use of - Google Patents
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002131 composite material Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000011065 in-situ storage Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 238000000935 solvent evaporation Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000010815 organic waste Substances 0.000 abstract description 3
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 52
- 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 description 19
- 229960000907 methylthioninium chloride Drugs 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000002835 absorbance Methods 0.000 description 18
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 229910001023 sodium amalgam Inorganic materials 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000002127 nanobelt Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- -1 insoluble matters Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002834 transmittance Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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 provides SnO prepared by redox mechanism2@Fe2O3A method of nano-photocatalytic composite material, comprising: mixing nano SnO2Dispersing in liquid phase medium to obtain SnO2A dispersion liquid; SnO reaction in the presence of a reducing agent2Nano SnO in dispersion liquid2The Sn (IV) on the surface is reduced into a low oxidation state of tin to obtain SnO2Reducing liquid; the above-mentioned SnO2Reducing solution and Fe2O3The solution is mixed evenly and reacts fully, and the product is separated, thus obtaining SnO2@Fe2O3A nano photocatalytic composite material. The method has the advantages of simple operation, short time, low cost, environmental protection, good repeatability, high efficiency, rapid and effective preparation of the nano photocatalytic composite material, and universality and large-scale production value. The nano photocatalytic composite material SnO prepared by the invention2@Fe2O3Has good ultraviolet-visible absorption range, greatly improves the photocatalytic degradation efficiency, and has broad application prospect in the fields of treating water pollution and organic waste.
Description
Technical Field
The present invention belongs to a nano photocatalysis composite materialThe technical field of material preparation, in particular to a novel photocatalytic material SnO2@Fe2O3Preparation and application of the compound.
Background
At present, domestic sewage, industrial wastewater, pesticide wastewater and the like seriously harm the life and even the life safety of people, but the traditional sewage treatment method can only remove pollutants such as insoluble matters, sand and the like in the sewage through a filtering technology, but has low treatment efficiency and high cost for soluble organic wastes and even can not achieve the ground of treatment.
However, series problems of complexity, poor stability, low catalytic degradation efficiency and the like exist in the preparation steps of the existing photocatalytic composite material.
SnO2The photocatalyst has the advantages of good visible light transmittance, low resistivity, stable chemical performance, strong acid and alkali resistance at room temperature and the like, so that the photocatalyst can be used as a photocatalytic material. However, pure state photocatalytic materials are difficult to satisfy all the requirements in the aspect of photocatalysis, and a novel photocatalyst must be designed and synthesized in order to improve the photocatalytic activity and efficiency. SnO2@Fe2O3The nano photocatalytic composite material has excellent photocatalytic activity in the UV-VIS range, shows a specific microstructure and is potential novel high-efficiency photocatalytic materials.
Disclosure of Invention
In order to overcome the defects, the invention adopts interfacial redox in-situ growth methods, and the method has the advantages of simple operation, short time, low cost, environmental friendliness, good repeatability, high efficiency and universality and large-scale production value.
In order to achieve the purpose, the invention adopts the following technical scheme:
SnO prepared by redox mechanism2@Fe2O3A method of nano-photocatalytic composite material, comprising:
mixing nano SnO2Dispersing in liquid phase medium to obtain SnO2A dispersion liquid;
SnO reaction in the presence of a reducing agent2Nano SnO in dispersion liquid2The Sn (IV) on the surface is reduced into a low oxidation state of tin to obtain SnO2Reducing liquid;
the above-mentioned SnO2Reducing solution and Fe2O3The solution is mixed evenly and reacts fully, and the product is separated, thus obtaining SnO2@Fe2O3A nano photocatalytic composite material.
Preferably, the liquid phase medium is water or an organic solvent.
Preferably, the reducing agent is any reducing agent capable of reducing sn (iv).
Preferably, the tin has a lower oxidation state of 0 or + 2.
Preferably, the SnO2Reducing solution and Fe2O3The solution undergoes redox reaction under the conditions of oscillation, ultrasound or stirring.
Preferably, the nano SnO2、Fe2O3The molar ratio of (a) to (b) is 1: x (x is 0.01 to 1).
Preferably, the SnO2The concentration of the dispersion is 0.1-100 mg/mL,
preferably, said Fe2O3The concentration of (b) is 0.1-100 mg/mL.
Preferably, the method for separating the product is centrifugation, filtration, sedimentation or solvent evaporation.
The invention also provides SnO prepared by the method of any 2@Fe2O3Nano photocatalytic composite material, said SnO2@Fe2O3The particle size of the nano photocatalytic composite material is at least D which is 1-100 nm.
The invention also provides the application of the catalyst composite material in the photocatalytic treatment of domestic sewage, industrial wastewater or pesticide wastewater.
The invention has the advantages of
(1) The method has the advantages of simple operation, short time, low cost, environmental friendliness, good repeatability, high efficiency, rapid and effective preparation of the nano photocatalytic composite material, and universality and large-scale production value.
(2) Tin dioxide has a forbidden band width of 3.5eV, and light absorption is in the ultraviolet region, while ferric oxide has a forbidden band width of 2.2eV, and light absorption is in the visible region. The nano photocatalytic composite material SnO prepared by the invention2@Fe2O3The method widens the spectrum absorption range, has good ultraviolet-visible absorption, greatly improves the photocatalytic degradation efficiency, and is beneficial to the application in the fields of treating water pollution and organic waste.
(3) The preparation method is simple, high in treatment efficiency, strong in practicability and easy to push .
Drawings
The accompanying drawings, which form a part hereof , are included to provide a further understanding of the present application, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the application and together with the description serve to explain the application and not limit the application.
FIG. 1 is SnO2@Fe2O3X-ray diffraction spectrum of the nano photocatalytic composite material.
FIG. 2 is SnO2@Fe2O3Transmission electron microscope picture (the scale bar in the picture is 50nm) of the nano photocatalytic composite material.
FIG. 3A is SnO2Photodegradation methylene blue ultraviolet absorption diagram of nano material, B is SnO2@Fe2O3The photodegradation methylene blue ultraviolet absorption pattern of the nano photocatalytic composite material (continuous irradiation of sunlight for 5 hours).
FIG. 4 is a graph of the concentration of methylene blue and the time variation obtained by measuring the absorbance of the nano material and the composite material solution thereof at different times and comparing the absorbance with the absorbance of the solution at the initial time.
Detailed Description
It is noted that the following detailed description is exemplary and is intended to provide further explanation of the invention at unless otherwise indicated.
Except for the difference in the preparation of the nano photocatalytic composite material, the application aspect of the nano photocatalytic composite material is that the condition of photocatalytic degradation of methylene blue is completely .
preparation of nano-photocatalytic composite material SnO by utilizing interface redox principle2@Fe2O3The method comprises the following steps:
1) dispersing the nano material in a proper solvent, and performing ultrasonic dispersion treatment;
2) adding a reducing agent into the dispersed solution, and oscillating, stirring or ultrasonically reducing the high oxidation state on the surface of the reactant fully;
3) adding Fe with nanometer level into the reduced solution2O3The solution is oscillated, stirred or ultrasonically treated to fully react, and then reactants are centrifugally separated, washed and dried to obtain SnO2@Fe2O3A nano photocatalytic composite material.
Preferably, the nano material in the step (1) is SnO2The nano-semiconductor material, tin dioxide, has a variety of structures ranging from zero-dimensional nanoparticles, -dimensional nanowires, nanorods, nanobelts, nanotubes, to three-dimensional nanospheres, nanocubes, etc. the different shapes of nanomaterials result in different properties and effects.
Preferably, the reducing agent in step (2) is any reducing agent capable of reducing sn (iv).
The principle of the invention is that the Sn on the surface of the nanometer material exists in a +4 oxidation state, and the Sn (IV) can be reduced to a low oxidation state (+2, 0) of tin by being reduced by a proper reducing agent, and the reaction formula is as follows:
Sn4++2e-＝Sn2+
Sn2++2e-＝Sn
then adding Fe2O3，Fe2O3Fe (III) in (1), (III) having oxidizing property, Fe when Sn in low valence state is oxidized into stable Sn (IV)3+Is reduced to Fe2+。
Fe at redox site2O3In-situ growth on nano-material SnO2Surface formation of stabilized SnO2@Fe2O3As can be seen from the electron micrograph of FIG. 2, the heterojunction composite material is combined more closely, and the bifunctional material is effectively integrated in .
Example 1:
(1) SnO2The nano particles are dispersed in ethanol solution to prepare 0.1mg/mL solution.
(2) Taking 4mL of the solution dispersed in the step (1), performing ultrasonic treatment for 10min under the ultrasonic power of 50W, adding 8 drops of prepared sodium amalgam, and oscillating for 10 min.
(3) Removing the sodium amalgam from the solution of step (2), adding 4 drops of 2mg/mLFe2O3And (3) putting the solution in the reduced ethanol solution, and performing ultrasonic treatment for 8min at the ultrasonic power of 50W. Centrifugal separation to obtain SnO2@Fe2O3The nano photocatalytic composite material, TEM dispersed in ethanol is shown in figure 2, and XRD analysis of the nano material is shown in figure 1.
(4) SnO to be prepared2Nanoparticles, SnO2@Fe2O32mg of the composite material is respectively dissolved in 20mL of methylene blue (10mg/L) solution;
(5) oscillating the solution in the dark for 10min to ensure that the photocatalyst-pollutant molecules reach adsorption-desorption balance in the aqueous solution;
(6) irradiating the above solution under 200W xenon lamp, centrifuging at intervals of 1h, collecting supernatant 3mL, measuring absorbance with ultraviolet-visible spectrophotometer, and the absorbance curves at different times are shown in FIGS. 3A and 3B. The absorbance of the solution at different times was measured and compared with the absorbance of the solution at the initial time to obtain the change of the concentration of methylene blue with time as shown in fig. 4. The results show that after 5 hours pure SnO2The degradation rate of methylene blue is 40 percent, and SnO2@Fe2O3The degradation rate of the heterojunction photocatalytic material to methylene blue reaches 60 percent。
SnO in the above (1)2Nanoparticles were purchased from alatin reagent.
Example 2:
(1) taking SnO2The nano particles are dispersed in ethanol solution to prepare 0.1mg/mL solution.
(2) Taking 4mL of the solution dispersed in the step (1), performing ultrasonic treatment for 8min under the ultrasonic power of 50W, adding 6 drops of 4mg/mL sodium borohydride solution, and oscillating for 10 min.
(3) Centrifuging the solution obtained in step (2), pouring out the supernatant, adding 4ml ethanol for re-ultrasonic dispersion, and adding 4 drops of 2mg/mLFe2O3Solution, ultrasonic reaction. Performing ultrasonic treatment for 10min with ultrasonic power of 100W. Filtering and separating to obtain SnO2@Fe2O3A nano photocatalytic composite material. It was shown that SnO2@Fe2O3The nano photocatalytic composite material can be stably synthesized under different ultrasonic powers and time, and provides a raw material for photocatalytic degradation of organic matters.
(5) SnO2Nanoparticles, SnO2@Fe2O32mg of the composite material is respectively dissolved in 20mL of methylene blue (10mg/L) solution;
(6) oscillating the solution in the dark for 10min to ensure that the photocatalyst-pollutant molecules reach adsorption-desorption balance in the aqueous solution;
(7) irradiating the solution under a 200W xenon lamp, centrifuging at intervals of 1h, taking 3mL of supernatant, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain absorbance curves at different times. And measuring the absorbance of the solution at different times, and comparing the absorbance with the absorbance of the solution at the initial moment to obtain the concentration and time change of the methylene blue. The results show that after 5 hours pure SnO2The degradation rate of methylene blue is 35 percent, and SnO2@Fe2O3The degradation rate of the heterojunction photocatalytic material to methylene blue reaches 55%.
Example 3:
(1) taking SnO2The nano particles are dispersed in ethanol solution to prepare 0.1mg/mL solution.
(2) Taking 4mL of the solution dispersed in the step (1), performing ultrasonic treatment for 8min under the ultrasonic power of 50W, adding 8 drops of prepared sodium amalgam, and oscillating for 10 min.
(3) Removing the sodium amalgam from the solution of step (2), adding 4 drops of 2mg/mLFe2O3And (3) putting the solution in the reduced ethanol solution, and performing ultrasonic treatment for 10min at the ultrasonic power of 50W. Evaporating the solvent to obtain SnO2@Fe2O3A nano photocatalytic composite material. It was shown that SnO2@Fe2O3The nano photocatalytic composite material can be stably synthesized under different ultrasonic powers and time, and provides a raw material for photocatalytic degradation of organic matters.
(5) SnO2Nanoparticles, SnO2@Fe2O32mg of the composite material is respectively dissolved in 20mL of methylene blue (10mg/L) solution;
(6) oscillating the solution in the dark for 10min to ensure that the photocatalyst-pollutant molecules reach adsorption-desorption balance in the aqueous solution;
(7) irradiating the solution under a 200W xenon lamp, centrifuging at intervals of 1h, taking 3mL of supernatant, and measuring absorbance by using an ultraviolet-visible spectrophotometer to obtain absorbance curves at different times. And measuring the absorbance of the solution at different times, and comparing the absorbance with the absorbance of the solution at the initial moment to obtain the concentration and time change of the methylene blue. The results show that after 5 hours pure SnO2The degradation rate of methylene blue is 30 percent, and SnO2@Fe2O3The degradation rate of the heterojunction photocatalytic material to methylene blue reaches 47%.
Example 4:
(1) SnO2The nanobelts were dispersed in ethanol solution to make 0.1mg/mL solution.
(2) Taking 4mL of the solution dispersed in the step (1), performing ultrasonic treatment for 10min under the ultrasonic power of 50W, adding 6 drops of 4mg/mL sodium borohydride solution, and oscillating for 10 min.
(3) Centrifuging the solution obtained in step (2), pouring out the supernatant, adding 4ml ethanol for re-ultrasonic dispersion, and adding 4 drops of 2mg/mLFe2O3Solution, ultrasonic reaction. Performing ultrasonic treatment for 5min with ultrasonic power of 100W. Thus obtaining SnO2@Fe2O3A nano photocatalytic composite material. Shows that different reducing agents and SnO with different shapes are adopted under different ultrasonic powers and times2The oxidation-reduction method can be used for stably synthesizing SnO2@Fe2O3A nano photocatalytic composite material.
(5) SnO2Nanobelt, SnO2@Fe2O3Respectively dissolving 2mg of the composite material in 20mL of methylene blue (10mg/L) solution;
(6) oscillating the solution in the dark for 10min to ensure that the photocatalyst-pollutant molecules reach adsorption-desorption balance in the aqueous solution;
(7) the solution is irradiated under a 200W xenon lamp, and after 1 hour, the solution is centrifuged to take 3mL of supernatant, and the absorbance of the supernatant is measured by using an ultraviolet-visible spectrophotometer. The results show that after 5 hours pure SnO2The degradation rate of methylene blue is 28 percent, and SnO2@Fe2O3The degradation rate of the heterojunction photocatalytic material to methylene blue reaches 45%.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
- SnO prepared by interface redox in-situ growth method 1 and 2@Fe2O3A method of preparing a nano-photocatalytic composite material, comprising:mixing nano SnO2Dispersing in liquid phase medium to obtain SnO2A dispersion liquid;SnO reaction in the presence of a reducing agent2Nano SnO in dispersion liquid2The positive quadrivalent Sn on the surface is reduced into the low oxidation state of the tin to obtain SnO2Reducing liquid;the SnO2Reducing solution and Fe2O3The solution is mixed evenly and reacts fully, and the product is separated, thus obtaining SnO2@Fe2O3A nano photocatalytic composite material;the nano SnO2、Fe2O3The molar ratio of (A) to (B) is 1: 0.01-1.
- 2. SnO prepared by interfacial redox in-situ growth method as defined in claim 12@Fe2O3The method for preparing the nano photocatalytic composite material is characterized in that the liquid phase medium is water or an organic solvent.
- 3. SnO prepared by interfacial redox in-situ growth method as defined in claim 12@Fe2O3The method for preparing the nano photocatalytic composite material is characterized in that the reducing agent is all reducing agents capable of reducing positive quadrivalent Sn.
- 4. SnO prepared by interfacial redox in-situ growth method as defined in claim 12@Fe2O3A method of nano-photocatalytic composite material, characterized in that the low oxidation state of the tin is 0 or + 2.
- 5. SnO prepared by interfacial redox in-situ growth method as defined in claim 12@Fe2O3A method of preparing a nano-photocatalytic composite material, wherein said SnO2Reducing solution and Fe2O3The solution undergoes redox reaction under the conditions of oscillation, ultrasound or stirring.
- 6. SnO prepared by interfacial redox in-situ growth method as defined in claim 12@Fe2O3A method of preparing a nano-photocatalytic composite material, wherein said SnO2The concentration of the dispersion is 0.1-100 mg/mL.
- 7. SnO prepared by interfacial redox in-situ growth method as defined in claim 12@Fe2O3Nano lightMethod for catalyzing a composite material, characterized in that said Fe2O3The concentration of the solution is 0.1-100 mg/mL.
- 8. SnO prepared by interfacial redox in-situ growth method as defined in claim 12@Fe2O3The method for separating the nano photocatalytic composite material is characterized in that the method for separating the product is centrifugation, filtration, sedimentation or solvent evaporation.
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| CN201710208046.6A CN107008336B (en) | 2017-03-31 | 2017-03-31 | photocatalytic materials SnO2@Fe2O3Preparation and use of |
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