CN111087013A - Black SnO2And preparation method and application thereof - Google Patents
Black SnO2And preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 14
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 12
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 239000010431 corundum Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 8
- 239000011941 photocatalyst Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 9
- 229940012189 methyl orange Drugs 0.000 abstract description 9
- 231100000331 toxic Toxicity 0.000 abstract description 7
- 230000002588 toxic effect Effects 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000032900 absorption of visible light Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000001048 orange dye Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 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 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of 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
- 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
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses black SnO2The preparation method comprises the following steps: SnCl4·5H2Dissolving O in hydrochloric acid to obtain solution A; dissolving NaOH in water to obtain a solution B; adding water into the container, heating in water bath, slowly adding the solution A and the solution B into the container at the same time, stirring, adjusting the pH value of the system to 6-7 by hydrochloric acid, and curing in an oven; taking out the solid in S1, drying, placing in a muffle furnace, controlling the temperature rise speed, heating to 400-800 deg.C to obtain white SnO2(ii) a Reacting NaBH4White SnO2Uniformly mixing and grinding, placing in a tube furnace, annealing at the temperature of 350-nO2. The black SnO with high visible light catalytic activity rate prepared by the invention2The method has the advantages of no use of toxic and harmful raw materials, short production period, strong absorption of visible light, and effective catalytic degradation of methyl orange pollutant molecules in water.
Description
Technical Field
The invention relates to black SnO2A preparation method of nano material and application thereof in the field of photocatalysis, in particular to black SnO2And a preparation method and application thereof.
Background
Environmental pollution is a common concern in countries throughout the world. In China, along with the rapid development of industry and manufacturing industry, a large amount of toxic and harmful pollutants are manufactured all the time, and water pollution, especially dye wastewater discharged from chemical plants, seriously threatens the environment and human health. The use of semiconductor photocatalysts to degrade these organic pollutants can degrade organic waste into CO2、H2The removal of toxic and harmful pollutants in water and soil by photocatalytic technology is considered to be one of effective means for solving the problem of environmental protection.
SnO2Is a typical n-type semiconductor, has been proved to have excellent photocatalytic performance and has wide application prospect in the field of water treatment. Due to SnO2The forbidden band width of the photocatalyst is 3.6eV, and ultraviolet light with higher energy is needed to effectively excite the photocatalytic reaction, so that the photocatalytic degradation efficiency of the photocatalyst is far lower than that of TiO2And ZnO, and the like. Thus, there is currently literature on promoting SnO2Mainly by doping metals and non-metals or by doping SnO2The method is compounded with other semiconductors to improve the light absorption characteristic and further obtain the photocatalytic degradation activity under the irradiation of visible light, but the operations are relatively complex, cumbersome and high in cost, toxic and harmful wastes are generated, and the industrial popularization and application of the method are limited. For example, Chinese patent publication No. CN 103406159A reports a photochemically prepared SnO2The graphene composite material has potential application prospect in the aspect of photocatalytic degradation of organic pollutants in water; chinese invention patent (publication No. CN 103881122A) reports a nano SnO with high visible light catalytic activity2The polyvinyl chloride composite film shows excellent light under visible lightThe performance of the dye rhodamine B in the water body is catalytically degraded, and meanwhile, the composite film is extremely easy to separate and recover from the degradation liquid, and has high stability.
Therefore, the development process flow is simple, the environment is friendly, and the SnO with high-efficiency visible light catalytic activity is developed2Materials remain a serious problem. Relevant documents and patents related to the stannic oxide photocatalyst at home and abroad are researched and researched, and no report about a simple preparation method of black stannic oxide and application of the black stannic oxide in photocatalytic water treatment is found at present.
Disclosure of Invention
Based on the technical problems in the background introduction, the invention provides black SnO2The invention also discloses a preparation method and application thereof, and the black SnO with high visible light catalytic activity rate prepared by the invention2The method does not use toxic and harmful raw materials, has short production period, is a novel method for preparing the black tin dioxide photocatalytic material simply, quickly and on a large scale, has strong absorption on visible light, and can effectively catalyze and degrade methyl orange pollutant molecules in water.
The invention provides black SnO2The preparation method comprises the following steps:
s1, preparation of Sn (OH)4Amorphous precursor
SnCl4·5H2Dissolving O in dilute hydrochloric acid to obtain solution A; dissolving NaOH in water to obtain a solution B;
adding water into a container, heating to 90-98 ℃ in a water bath, slowly adding the solution A and the solution B into the container at the same time, stirring, adjusting the pH value of the system to 6-7 by hydrochloric acid, and conveying to an oven for curing;
s2 preparation of white SnO2
Taking out the solid in S1, removing the metal ions and hydrochloric acid adsorbed on the surface, drying, placing in a muffle furnace, heating to 400-800 ℃, and preserving heat to obtain white SnO2；
S3, preparing black SnO2
Reacting NaBH4White SnO2Mixing, grinding, placing in a tube furnace, in a protective atmosphere,annealing treatment at the temperature of 350-2。
The preparation process of the invention comprises the following steps:
1. preparation of Sn (OH)4Amorphous precursor, adding SnCl4·5H2The reason why O is dissolved in a dilute hydrochloric acid solution is selected to prevent Sn4+Hydrolyzing the ions, reacting the ions with NaOH in a water bath, and finally adjusting the pH value to be between 6 and 7.
2. Preparation of white SnO2Powder of Sn (OH) obtained in the previous step4High-temperature annealing treatment of the amorphous precursor precipitate in air to remove hydroxyl and crystal water, and crystallization at high temperature to obtain defect-free white SnO2And (3) powder.
3. Preparation of Black SnO2Powder, under protective atmosphere, by NaBH4Strong chemical reduction in white Ta2O5Introduction of Sn into crystal lattice2+Ions and oxygen vacancies narrow the band gap width, improve the absorption of visible light and finally obtain black SnO2。
Preferably, in S1, SnCl is added4·5H2Dissolving O in dilute hydrochloric acid, wherein the concentration of the dilute hydrochloric acid is 1-3 mol/L; preferably, SnCl4·5H2The weight volume ratio g of O to dilute hydrochloric acid is as follows: ml is 1-2: 25-50.
Preferably, in S1, NaOH is dissolved in water, wherein the weight to volume ratio of NaOH to water, g: ml is 2.5-5: 25-50.
Preferably, in S1, the curing temperature is more than or equal to 60 ℃ and the curing time is more than or equal to 24h in the curing process.
Preferably, in S1, water, wherein SnCl is added to the container4·5H2The weight volume ratio g of O to water: ml is 1-2: 100-300.
Preferably, after drying, the corundum crucible is firstly filled and then placed in a muffle furnace; preferably, the muffle ramp rate is 5-10 deg.C/min.
Preferably, in S3, NaBH4With white SnO2The mass ratio of (A) to (B) is more than or equal to 0.5: 1.
preferably, in S3, the shielding gas is nitrogen and/or argon.
The invention also provides the black SnO2The black SnO is adopted2The preparation method is as follows.
The invention also provides the black SnO2Application in photocatalyst.
Black SnO with high visible light catalytic activity rate2The preparation method of (1). The simple wet chemical method is mainly adopted to prepare Sn (OH)4Amorphous precursor is calcined in air at high temperature to prepare white SnO2. Followed by NaBH4As a reducing agent, reducing white SnO at high temperature under the condition of protective gas2Black SnO is obtained2A photocatalytic material. The specific principle is that the oxide is prepared by reacting SnO2Low-valence Sn is introduced into crystal lattice2+Ion and oxygen vacancy defects, making SnO2The band gap is narrowed, so that the visible light in sunlight can be absorbed and utilized to expand the absorbance of the sunlight to visible light, the recombination probability of photo-generated electrons and holes is reduced, and the methyl orange pollutants in the water body are degraded by high-efficiency photocatalysis.
The preparation process does not use toxic and harmful raw materials, has short production period, is a novel method for simply, quickly and massively preparing the black tin dioxide photocatalytic material, has mature process and uniform product particle size, and can be used for large-scale industrial production. According to the invention, the dye methyl orange is taken as a photodegradation object, and research shows that the introduction of a defect structure improves SnO2The catalytic activity under visible light, the removal rate of methyl orange with the concentration of 10ppm in water within 30 minutes can reach 93.6 percent, and the result proves that the black SnO has the advantages of high catalytic activity, low cost and high catalytic activity2Has bright prospect in the aspect of being applied to water pollution treatment.
The black SnO prepared by the invention2The photocatalyst has the following advantages:
1. the raw material used in the synthesis process comprises SnCl4·5H2O, hydrochloric acid, NaOH and NaBH4The inside is a bulk chemical, is cheap and easily available, is friendly to human body and environment, and cannot cause pollution and damage;
2. the wet chemistry and calcination preparation process is adopted, the flow is simple and easy to operate, and industrial equipment can be used for mass synthesis;
3. the resulting black SnO2The catalyst has strong absorption to visible light, and can effectively catalyze and degrade methyl orange pollutant molecules in water.
Drawings
FIG. 1 is a white SnO prepared in example 52And black SnO2A photograph of the sample of (1);
FIG. 2 is a black SnO prepared in example 52A TEM photograph of;
FIG. 3 is black SnO prepared in example 52The absorption spectrum of the powder;
FIG. 4 is a black SnO prepared in example 52Electron paramagnetic resonance spectroscopy of (1);
FIG. 5 is a black SnO prepared in example 52And (3) catalytically degrading the methyl orange dye in the water body under the irradiation of visible light.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Black SnO2The preparation method comprises the following steps:
s1, preparation of Sn (OH)4Amorphous precursor
1g of SnCl4·5H2Dissolving O in dilute hydrochloric acid with the volume of 25mL to obtain solution A;
dissolving 2.5g of NaOH in 25mL of deionized water to obtain a solution B;
adding 100ml of deionized water into a container, heating to 90 ℃ in a water bath, slowly adding the solution A and the solution B into the container at the same time, stirring for 2min, adjusting the pH value of the system to be 6 by using dilute hydrochloric acid, conveying the system into an oven for curing, wherein the curing temperature is 60 ℃, and the curing time is 24 h;
s2 preparation of white SnO2
Taking out the solid in S1, washing with deionized water and ethanol repeatedly to remove metal ions and hydrochloric acid adsorbed on the surface, drying, placing into corundum crucible, placing into muffle furnace, and controllingThe temperature rising speed is 5 ℃/min, the temperature is raised to 400 ℃, and the temperature is kept for 2h to obtain white SnO2；
S3, preparing black SnO2
0.5g of NaBH41g of white SnO2Mixing, grinding, placing in a corundum crucible, annealing at 350 deg.C for 0.5 hr in nitrogen atmosphere, taking out after the temperature in the furnace is reduced to room temperature, washing with deionized water and methanol for 3 times to remove excessive unreacted NaBH4Then the mixture is sent into a baking oven and dried at the temperature of 60 ℃ to obtain black SnO2。
Example 2
Black SnO2The preparation method comprises the following steps:
s1, preparation of Sn (OH)4Amorphous precursor
2g of SnCl4·5H2Dissolving O in dilute hydrochloric acid with the volume of 50mL to obtain solution A;
dissolving 5g of NaOH in 50mL of deionized water to obtain a solution B;
adding 300ml of deionized water into a container, heating to 98 ℃ in a water bath, slowly adding the solution A and the solution B into the container at the same time, stirring for 10min, adjusting the pH value of the system to 7 by using dilute hydrochloric acid, conveying the system into an oven for curing, wherein the curing temperature is 90 ℃, and the curing time is 40 hours;
s2 preparation of white SnO2
Taking out the solid in S1, washing with deionized water and ethanol repeatedly to remove metal ions and hydrochloric acid adsorbed on the surface, drying, placing into a corundum crucible, heating to 780 deg.C in a muffle furnace at a temperature rising speed of 10 deg.C/min, and maintaining for 4h to obtain white SnO2；
S3, preparing black SnO2
2g of NaBH41g of white SnO2Mixing, grinding, placing into corundum crucible, placing in tubular furnace, annealing at 385 deg.C for 2 hr under argon atmosphere, taking out after the temperature in furnace is reduced to room temperature, washing with deionized water and methanol for 3 times respectively to remove excessive unreacted NaBH4Is sent into a drying ovenDrying at 60 deg.C in a box to obtain black SnO2。
Example 3
Black SnO2The preparation method comprises the following steps:
s1, preparation of Sn (OH)4Amorphous precursor
1.2g SnCl4·5H2Dissolving O in a dilute hydrochloric acid with the volume of 30mL to obtain a solution A;
dissolving 3g of NaOH in 30mL of deionized water to obtain a solution B;
adding 200ml of deionized water into a container, heating to 94 ℃ in a water bath, slowly adding the solution A and the solution B into the container at the same time, stirring for 6min, adjusting the pH value of the system to 6.3 by using dilute hydrochloric acid, conveying the system into an oven for curing at the curing temperature of 70 ℃ for 28 h;
s2 preparation of white SnO2
Taking out the solid in S1, washing with deionized water and ethanol repeatedly to remove metal ions and hydrochloric acid adsorbed on the surface, drying, placing into a corundum crucible, heating to 600 deg.C at a controlled temperature rising speed of 8 deg.C/min in a muffle furnace, and maintaining for 3h to obtain white SnO2；
S3, preparing black SnO2
1g of NaBH41g of white SnO2Mixing, grinding, placing in a corundum crucible, placing in a tubular furnace, annealing at 380 deg.C for 1 hr under protective atmosphere with protective gas including nitrogen and argon, taking out after the temperature in the furnace is reduced to room temperature, washing with deionized water and methanol for 3 times respectively to remove excessive unreacted NaBH4Then the mixture is sent into a baking oven and dried at the temperature of 60 ℃ to obtain black SnO2。
Example 4
Black SnO2The preparation method comprises the following steps:
weighing 1g of SnCl4·5H2O solid powder, dissolved in 2mol/L dilute hydrochloric acid with the volume of 25mL, and slightly treated with ultrasound to form a transparent clear solution A. 2.5 grams of NaOH solid is weighed, dissolved in 25mL of deionized water,thus obtaining a solution B.
Adding 200mL of deionized water into a three-neck flask with the volume of 250mL, heating the mixture in a water bath to 95 ℃, simultaneously and slowly dripping the solution A and the solution B into the three-neck flask, continuously stirring the mixture for 5 minutes, and then adjusting the pH value to 6-7 by using dilute hydrochloric acid.
Aging the three-neck flask filled with the sol in a 60 ℃ oven for 24h, washing and drying white solid powder at the bottom of the flask, putting the white solid powder into a corundum crucible, putting the corundum crucible into a muffle furnace, heating to 400 ℃, keeping the temperature for 4h, stopping heating, and taking out white SnO when the temperature in the furnace is reduced to room temperature2And (3) powder.
1g of white SnO2Powder with 0.5g NaBH4Uniformly mixing, placing in a tube furnace, annealing at 350 ℃ for 1h under the protection of argon atmosphere, taking out after the temperature in the furnace is reduced to room temperature, washing with deionized water and methanol for 3 times respectively to remove redundant unreacted NaBH4Then dried in an oven at 60 ℃ to obtain black SnO2。
Example 5
Black SnO2The preparation method comprises the following steps:
weighing 2g of SnCl4·5H2O solid powder, dissolved in dilute hydrochloric acid with a volume of 50mL and a concentration of 2mol/L, and slightly sonicated to form a clear A solution. 5 grams of NaOH solid was weighed and dissolved in 50mL of deionized water to obtain solution B.
400mL of deionized water was added to a three-necked flask with a volume of 500mL, heated in a water bath to 95 deg.C, and the solution A and the solution B were added dropwise to the three-necked flask simultaneously and continuously with stirring for 10 minutes. Then dilute hydrochloric acid is used for adjusting the pH value to 6-7.
And (3) aging the three-neck flask filled with the sol in a 60 ℃ oven for 24h, washing and drying white solid powder at the bottom of the flask, filling the white solid powder into a corundum crucible, placing the corundum crucible in a muffle furnace, heating to 500 ℃, preserving heat for 4h, and stopping heating. When the temperature in the furnace is reduced to room temperature, taking out white SnO2And (3) powder.
1g of white SnO2Powder with 0.5g NaBH4MixingUniformly placing the mixture in a tube furnace, annealing at 400 ℃ for 0.5h under the protection of argon atmosphere, taking out the mixture after the temperature in the furnace is reduced to room temperature, and respectively washing the mixture for 3 times by using deionized water and methanol to remove redundant unreacted NaBH4Then dried in an oven at 60 ℃ to obtain black SnO2。
Referring to FIGS. 1-5, FIG. 1 shows white SnO prepared in example 52And black SnO2A photograph of the sample of (1); FIG. 2 is a black SnO prepared in example 52A TEM photograph of; FIG. 3 is black SnO prepared in example 52The absorption spectrum of the powder; FIG. 4 is a black SnO prepared in example 52Electron paramagnetic resonance spectroscopy of (1); FIG. 5 is a black SnO prepared in example 52The methyl orange dye in the water body is catalytically degraded under the irradiation of visible light. The preparation process does not use toxic and harmful raw materials, has short production period, is a novel method for preparing the black tin dioxide photocatalytic material simply, quickly and on a large scale, has mature process and uniform product particle size, and can realize large-scale industrial production2The catalytic activity under visible light, the removal rate of methyl orange with the concentration of 10ppm in water within 30 minutes can reach 93.6 percent, and the result proves that the black SnO has the advantages of high catalytic activity, low cost and high catalytic activity2Has bright prospect in the aspect of being applied to water pollution treatment.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. Black SnO2The preparation method is characterized by comprising the following steps:
s1, preparation of Sn (OH)4Amorphous precursor
SnCl4·5H2Dissolving O in dilute hydrochloric acid to obtain solution A; dissolving NaOH in water to obtain a solution B;
adding water into a container, heating to 90-98 ℃ in a water bath, slowly adding the solution A and the solution B into the container at the same time, stirring, adjusting the pH value of the system to 6-7 by hydrochloric acid, and conveying to an oven for curing;
s2 preparation of white SnO2
Taking out the solid in S1, removing the metal ions and hydrochloric acid adsorbed on the surface, drying, placing in a muffle furnace, heating to 400-800 ℃, and preserving heat to obtain white SnO2；
S3, preparing black SnO2
Reacting NaBH4White SnO2Uniformly mixing and grinding, placing in a tube furnace, annealing at the temperature of 350-400 ℃ in a protective atmosphere, and cooling to obtain black SnO2。
2. A black SnO according to claim 12Characterized in that, in S1, SnCl is added4·5H2Dissolving O in dilute hydrochloric acid, wherein the concentration of the dilute hydrochloric acid is 1-3 mol/L; preferably, SnCl4·5H2The weight volume ratio g of O to dilute hydrochloric acid is as follows: ml is 1-2: 25-50.
3. A black SnO according to claim 12Is characterized in that in S1, NaOH is dissolved in water, wherein the weight to volume ratio of NaOH to water g: ml is 2.5-5: 25-50.
4. A black SnO according to claim 12The preparation method is characterized in that in S1, in the curing process, the curing temperature is more than or equal to 60 ℃, and the curing time is more than or equal to 24 hours.
5. A black SnO according to claim 12Is characterized in that in S1, water is added into a container, wherein SnCl is4·5H2The weight volume ratio g of O to water: ml is 1-2: 100-300.
6. A black SnO according to claim 12The preparation method of (1) is characterized in that, in S2, after drying, the corundum crucible is firstly filled in a corundum crucible and then placed in a muffle furnace; preferably, the muffle ramp rate is 5-10 deg.C/min.
7. A black SnO according to claim 12Characterized in that, in S3, NaBH is added4With white SnO2The mass ratio of (A) to (B) is more than or equal to 0.5: 1.
8. a black SnO according to claim 12The method of (5), wherein in S3, the shielding gas is nitrogen and/or argon.
9. A black SnO according to claim 12Characterized in that a black SnO according to any of claims 1 to 8 is used2The preparation method is as follows.
10. A black SnO as claimed in claim 92Application in photocatalyst.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111960464A (en) * | 2020-08-28 | 2020-11-20 | 陕西科技大学 | Black titanium dioxide light nano material rich in oxygen vacancy defects and preparation method and application thereof |
| CN112723408A (en) * | 2020-12-27 | 2021-04-30 | 苏州机数芯微科技有限公司 | SnO2/MoSe2Composite material and preparation method and application thereof |
-
2019
- 2019-12-25 CN CN201911354594.5A patent/CN111087013A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| WUJIE DONG ET AL.: ""A Robust and Conductive Black Tin Oxide Nanostructure akes Efficient Lithium-Ion Batteries Possible"", 《ADV. MATER.》 * |
| ZHENG-WEI ZHOU ET AL.: ""Elaborate synthesis of black tin oxide–black titanium oxide core–shell nanotubes for ultrastable and fast lithium storage"", 《CHEM. COMMUN.》 * |
| 周正华: "《纳米材料开发使用及质量检测技术标准应用手册》", 30 April 2005, 银声音像出版社 * |
| 梁燕萍等: "《大学实验化学》", 28 February 2017, 西安电子科技大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111960464A (en) * | 2020-08-28 | 2020-11-20 | 陕西科技大学 | Black titanium dioxide light nano material rich in oxygen vacancy defects and preparation method and application thereof |
| CN111960464B (en) * | 2020-08-28 | 2023-04-28 | 陕西科技大学 | Black titanium dioxide optical nano material rich in oxygen vacancy defects and preparation method and application thereof |
| CN112723408A (en) * | 2020-12-27 | 2021-04-30 | 苏州机数芯微科技有限公司 | SnO2/MoSe2Composite material and preparation method and application thereof |
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