CN113750984B - Controllable hierarchical porous SnO 2 Preparation method of/C photocatalyst - Google Patents
Controllable hierarchical porous SnO 2 Preparation method of/C photocatalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 20
- 229910006404 SnO 2 Inorganic materials 0.000 title claims description 20
- 239000002114 nanocomposite Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 21
- NJASUIDIZMMYED-UHFFFAOYSA-N tetra(propan-2-yl)stannane Chemical compound CC(C)[Sn](C(C)C)(C(C)C)C(C)C NJASUIDIZMMYED-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000004108 freeze drying Methods 0.000 claims abstract description 13
- 229930006000 Sucrose Natural products 0.000 claims abstract description 11
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 11
- 239000005720 sucrose Substances 0.000 claims abstract description 11
- 229960000583 acetic acid Drugs 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000084 colloidal system Substances 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 128
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 49
- 239000000377 silicon dioxide Substances 0.000 abstract description 24
- 229910052681 coesite Inorganic materials 0.000 abstract description 23
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 23
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 23
- 229910052682 stishovite Inorganic materials 0.000 abstract description 23
- 229910052905 tridymite Inorganic materials 0.000 abstract description 23
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 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 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 8
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- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000003403 water pollutant Substances 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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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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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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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
- C02F2101/308—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
A controllable hierarchical porous SnO2/C photocatalyst preparation method relates to a photocatalyst preparation method, which comprises the steps of firstly, synthesizing tin-oxygen clusters by taking tetraisopropyl tin as a tin source, mixing with glacial acetic acid according to a volume ratio, stirring to form milky suspension, centrifugally collecting precipitate, and drying to obtain a precursor of SnO2. And step two, uniformly mixing the SnO2 precursor, sucrose and SiO2 colloid solutions with different masses, freeze-drying, collecting white powder, and performing high-temperature annealing to obtain the SnO2/C nanocomposite. Step three: and etching with NaOH solution to remove SiO2, washing with deionized water to neutrality, and obtaining the hierarchical porous SnO2/C nanocomposite. The method can optimize the microstructure of SnO2/C, including pore size, specific surface area and the like, can effectively prepare a layered and interconnected pore structure, has stable photocatalytic performance, is simple in preparation method, has an adjustable hierarchical porous structure, and the obtained composite material has excellent photocatalytic performance.
Description
Technical Field
The invention relates to a preparation method of a photocatalyst, in particular to a preparation method of a controllable hierarchical porous SnO2/C photocatalyst.
Background
With the rise of the energy industry, environmental pollution is also becoming serious, wherein dye wastewater from textile, dye manufacturing and printing industries has carcinogenic and mutagenic effects on humans and animals. In the recent work of repairing dye wastewater, we have explored and tried in adsorption, filtration, photocatalytic oxidation, electrochemical destruction, etc. Among various degradation schemes, the heterojunction photocatalytic oxidation method is outstanding, has high removal efficiency, is simple to use and environment-friendly, and is recognized as the most common and promising method for removing dye wastewater. In the process of photocatalytic degradation of dye, the heterojunction structure in the compound semiconductor catalyst can effectively promote separation of charges and holes, accelerate transportation of charges on the heterojunction, and simultaneously reduce recombination quenching of the charges and the holes, so that photocatalytic degradation efficiency is improved.
n-type semiconductor SnO 2 The electron band structure of the (C) has profound utilization value and research significance in the fields of electrochemistry, photoelectrochemistry and photocatalysis, has extremely high photogenerated hole oxidation potential (3.21V vs. NHE), extremely low photogenerated electron reduction potential (-0.39V vs. NHE), can meet the requirements of various photocatalytic oxidation and reduction reactions, and therefore SnO 2 Have been used for photocatalytic reduction of water pollutants. But due to its wider bandgap, snO 2 Only by photons of ultraviolet light, i.e. only 5% of the ultraviolet light in solar energy, which makes its use limited.
To widen the photoresponse range, researchers have tried to make SnO 2 Doped with metal ions and non-metals (such as Sn 2+ Self-doping or formation of oxygen vacancies, with g-C 3 N 4 、Fe 2 O 3 、CdS、ZnO、TiO 2 Isodoping to form nanocomposite catalysts with small bandgap photocatalysts), reducing SnO 2 Particle size, etc. However, we found Sn 2+ Introduction of oxygen vacancies leads to lattice distortion (reduced stability), g-C 3 N 4 /SnO 2 The composite material has still unsatisfactory photocatalytic activity due to the limited electron-hole separation efficiency, while SnO 2 Doping with other metal compounds typically uses a water/solvothermal process, requiring expensive autoclaves and not precise control of crystal growth. On the other hand, in reducing SnO 2 In the study of particle size, snO 2 Nanoparticles often exhibit microporosity, limiting adsorption and diffusion of most dyes, and are not accessible to some organic macromolecules, which adversely affects subsequent photocatalytic degradation reactions.
Disclosure of Invention
The invention aims to provide a controllable hierarchical porous SnO2/C photocatalyst preparation method, which optimizes the microstructure of SnO2/C, provides proper annealing conditions, pore size distribution and a steady interface, provides high surface area and rich reaction centers for photodegradation of pollutants, promotes separation of photon-generated carriers, and has low cost and easy industrial application.
The invention aims at realizing the following technical scheme:
a method for preparing a controllable hierarchical porous SnO2/C photocatalyst, which comprises the following preparation processes:
1) Using tetraisopropyl tin as a tin source, and mixing glacial acetic acid and tetraisopropyl tin according to a volume ratio of 10:1, mixing; stirring the solution at room temperature to form a milky suspension, centrifuging to obtain a white precipitate, and vacuum drying at 65 ℃ to obtain a precursor of SnO 2;
2) Mixing the sample prepared in the step 1 with 0.3 g sucrose and a certain amount of SiO2 colloidal solution with different particle sizes, adding 3 mL deionized water into the mixed solution to dissolve the mixture, and uniformly mixing;
3) Rapidly freezing with liquid nitrogen, then freeze-drying 12-h, collecting white powder after freeze-drying, placing a composite material precursor in an inert atmosphere, and obtaining the SnO2/C nanocomposite under different annealing conditions;
4) Etching the material by using NaOH solution to remove SiO2, and then washing the material to be neutral by using deionized water;
5) And adding SnO2 synthesized by SnCl4 and commercial SnO2 into the control group as different tin sources to carry out blank control, and repeating the step 3 to obtain the SnO2 nanomaterial without double templates under different precursor conditions.
The SiO2 size of the template in the step 2 is 0nm (not added), 7 nm (30 wt%,1.1 g), 12 nm (30 wt%,1.1 g) and 22 nm (40 wt% and 0.75 g).
According to the preparation method of the controllable hierarchical porous SnO2/C photocatalyst, the temperature of the precursor annealing condition in the step 3 is 500-1000 ℃ and the time is 1-7 hours.
The preparation method of the controllable hierarchical porous SnO2/C photocatalyst comprises the step 5, wherein a hollow white control precursor tin source is SnCl4 or commercial SnO2.
The invention has the advantages and effects that:
1. in the invention, snO2/C nano composite materials with interconnection pore structures are manufactured on three different scales by taking metal oxygen clusters as precursors and combining ice and a hard template. Tetraisopropyl tin prepared by sol-gel technology is used as a stoichiometric controlled tin source. In this work, colloidal silica having SiO2 of varying mass concentration can be used to tailor the mesopores of interconnected layered SnO2/C nanocomposites, and the ice templating approach can enable integration of pore structures with tunable morphology features into the nanocomposite. In addition to SnO2, the method is also applicable to the production of other materials for energy related applications with enhanced electrochemical properties.
2. The invention has higher photocatalytic activity, and under the existence of SnO2/C nano catalyst: the degradation of methylene blue under the irradiation of ultraviolet/visible light is about 1.88/5.56 times and 6.37/3.72 times of SnO2 synthesized by a standard photocatalyst SnCl4, the SnO2/C nanocomposite prepared by the silica template shows good photoelectrochemical property with the optical flow density of 6.2 mA/cm < 2 > under the annealing condition of 900 ℃ and 5 hours, and the photocatalytic property of the SnO2/C nanocomposite prepared by the preparation method is very stable. The preparation method is simple, the appearance is unique, and the obtained composite material has excellent photodegradation and photoelectric conversion performance.
3. The SnO2/C nanocomposite with the tetraisopropyl tin as a tin source has the effect superior to that of a composite with SnO2 synthesized by SnCl4 and commercial SnO2 as a tin source; the photoreactivity of the SnO2/C nanocomposite is very stable, and the method is suitable for actual industrial production; preparing a hierarchical porous structure with the combination of macropores, mesopores and micropores by a simple dual-template method, wherein the pore ratio can be regulated and controlled; the method can be widely applied to the preparation of other semiconductor composite materials.
4. The invention discloses a controllable preparation hierarchical porous SnO 2 A dual-template method of the/C photocatalyst can utilize SiO 2 Designing a template to obtain the hierarchical porous SnO 2 Solves the problem of low porosity of most of the composites, and enhances the adsorption of the catalyst to the dye in water. In addition, glucose is used as a template to provide a carbon source for the composite catalyst, and SnO is formed 2 The catalyst has larger specific surface area while the heterojunction structure is formed, so that rich reaction centers are provided for the photodegradation of the heterojunction interface, the separation of photon-generated carriers is promoted, and the degradation is finally achieved.
Drawings
FIG. 1a is a graph showing the degradation of MB under UV light of each catalyst under different sized SiO2 templates of the present invention versus a blank different tin source catalyst;
FIG. 1b is a graph comparing MB degradation under visible light for each catalyst under different sized SiO2 templates of the present invention with a blank different tin source catalyst;
FIG. 1c is a graph of the current density potential (J-V) of the catalyst in visible light (embedded with corresponding open circuit curve) for different sized SiO2 templates of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples are only for illustrating the technical scheme of the present invention and should not be construed as limiting the contents of the claims of the present invention.
In the following examples, the raw materials used are conventional commercial products, and the reagents such as tetraisopropyl tin, glacial acetic acid, snCl4 and the like are purchased from national pharmaceutical chemicals Co., ltd; the equipment used is conventional equipment, and the testing method is conventional. The application of the dual-template preparation method for the controllable preparation of the hierarchical porous SnO2/C photocatalyst in degrading methylene blue dye and the excellence of the photoelectrochemical property are further described.
Example 1
A double-template method for preparing a hierarchical porous SnO2/C photocatalyst is controllable, siO2 with different particle sizes is used as a hard template, and the influence of mesoporous size on the activity of the catalyst is regulated, and the method comprises the following preparation processes:
1) Synthesis of tin oxide cluster with tetraisopropyl tin as tin source, glacial acetic acid and tetraisopropyl tin at 10:1, mixing the components in a volume ratio; stirring the solution at room temperature to be changed into milky suspension, centrifugally collecting precipitate, and then drying in vacuum at 65 ℃ to obtain a precursor of SnO 2;
2) Mixing 0.8 g of SnO2 precursor and 0.3 g sucrose and 0nm (without addition), 7 nm (30 wt%,1.1 g), 12 nm (30 wt%,1.1 g), 22 nm (40 wt%,0.75 g) SiO2 colloidal solution, ensuring that the mass ratio of sucrose to SiO2 is 1:1, a step of; adding 3 ml deionized water into the mixed solution to dissolve the mixture;
3) Rapidly freezing with liquid nitrogen, then freeze-drying 12 h, collecting white powder after freeze-drying, and annealing 5h at 900 ℃ to prepare the SnO2/C nanocomposite;
4) Etching the material with 3M NaOH solution at 80 ℃ for 24 h to remove SiO2, and then neutralizing the sample with deionized water to adjust the pH value;
the concentration and the dosage of the medicine for reaction degradation are as follows: 10-4 mol/L80 mL methylene blue solution, 25 mg SnO2/C nanocomposite.
In the embodiment, the degradation rate of the SnO2/C nanocomposite of the SiO2 template under the irradiation of ultraviolet light (40 wt percent, 0.75 g) on the photocatalytic reaction of methylene blue is 0.1672min < -1 >; and tetraisopropyl tin is superior to SnO2 synthesized from SnCl4 and commercial SnO2 as a tin source (see fig. 1 a).
In the embodiment, the degradation rate of the SnO2/C nanocomposite of the SiO2 template under the irradiation of visible light (40 wt percent, 0.75 g) on the photocatalytic reaction of methylene blue is 0.04131 min < -1 >; and tetraisopropyl tin is superior to SnO2 synthesized from SnCl4 and commercial SnO2 as a tin source (see fig. 1 b).
In this embodiment, the SnO2/C nanocomposite material of the SiO2 template has a photocurrent density of 6.2 mA/cm2 in a 1M Na2SO4 solution under irradiation of visible light (40 wt%,0.75 g) (see FIG. 1C)
Example 2
A dual-template method preparation method for controllable preparation of a hierarchical porous SnO2/C photocatalyst, which has different effects on catalyst activity due to different annealing conditions, the method comprises the following preparation processes:
1) Synthesis of tin oxide cluster with tetraisopropyl tin as tin source, glacial acetic acid and tetraisopropyl tin at 10:1, mixing the components in a volume ratio; stirring the solution at room temperature to be changed into milky suspension, centrifugally collecting precipitate, and then drying in vacuum at 65 ℃ to obtain a precursor of SnO 2;
2) Mixing 0.8 g of precursor of SnO2 with 0.3 g sucrose and 22 nm (40 wt%,0.75 g) of SiO2 colloidal solution, ensuring that the mass ratio of sucrose to SiO2 is 1:1, a step of; adding 3 ml deionized water into the mixed solution to dissolve the mixture;
3) Rapidly freezing with liquid nitrogen, then freeze-drying 12 h, freeze-drying, collecting white powder, and annealing at 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ and 1000 ℃ for 5h to prepare the SnO2/C nanocomposite;
4) The material was etched 24 h with 3M NaOH solution at 80 ℃ to remove SiO2, and then the sample was neutralized with deionized water to adjust pH.
The concentration and the dosage of the medicine for reaction degradation are as follows: 10-4 mol/L80 mL methylene blue solution, 25 mg SnO2/C nanocomposite.
In the embodiment, the degradation rate of the SnO2/C nanocomposite material on the photocatalytic reaction of the methylene blue under the condition of the annealing temperature of 900 ℃ under the irradiation of ultraviolet light is 0.1672min < -1 >.
In the embodiment, the degradation rate of the SnO2/C nanocomposite material on the photocatalytic reaction of methylene blue under the condition of 900 ℃ of annealing temperature under the irradiation of visible light is 0.04131 min < -1 >.
Example 3
A dual-template method preparation method for controllable preparation of a hierarchical porous SnO2/C photocatalyst, which has different influence conditions of annealing time on activity, the method comprises the following preparation processes:
1) Synthesis of tin oxide cluster with tetraisopropyl tin as tin source, glacial acetic acid and tetraisopropyl tin at 10:1, mixing the components in a volume ratio; stirring the solution at room temperature to be changed into milky suspension, centrifugally collecting precipitate, and then drying in vacuum at 65 ℃ to obtain a precursor of SnO 2;
2) Mixing 0.8 g of precursor of SnO2 with 0.3 g sucrose and 22 nm (40 wt%,0.75 g) of SiO2 colloidal solution, ensuring that the mass ratio of sucrose to SiO2 is 1:1, a step of; adding 3 ml deionized water into the mixed solution to dissolve the mixture;
3) Rapidly freezing with liquid nitrogen, then freeze-drying 12 h, collecting white powder after freeze-drying, and annealing at 900 ℃ for 1 h, 3 h, 5h and 7 h to prepare the SnO2/C nanocomposite;
4) The material was etched 24 h with 3M NaOH solution at 80 ℃ to remove SiO2, and then the sample was neutralized with deionized water to adjust pH.
The concentration and the dosage of the medicine for reaction degradation are as follows: 10-4 mol/L80 mL methylene blue solution, 25 mg SnO2/C nanocomposite.
In the embodiment, the degradation rate of the SnO2/C nanocomposite material on the methylene blue by the photocatalytic reaction under the condition of 5h annealing time under the irradiation of ultraviolet light is 0.1672min < -1 >.
In the embodiment, the degradation rate of the SnO2/C nanocomposite material on the photocatalytic reaction of methylene blue under the condition of 5h annealing time under the irradiation of visible light is 0.04131 min < -1 >.
Example 4
A dual-template preparation method for controllable preparation of a hierarchical porous SnO2/C photocatalyst, wherein different precursors are used as tin sources to influence the activity under a blank condition, and the method comprises the following preparation processes:
1) Synthesis of tin oxide cluster with tetraisopropyl tin as tin source, glacial acetic acid and tetraisopropyl tin at 10:1, mixing the components in a volume ratio; stirring the solution at room temperature, converting into milky suspension, centrifuging, collecting precipitate, and vacuum drying at 65deg.C to obtain SnO2 precursor, and simultaneously using SnO2 synthesized by using SnCl4 as tin source and commercial SnO2 as different precursors;
2) Mixing 0.8 g of three precursors of SnO2 with 0.3 g sucrose and 0nm (no addition) of SiO2 colloidal solution; adding 3 ml deionized water into the mixed solution to dissolve the mixture;
3) Rapidly freezing with liquid nitrogen, then freeze-drying 12 h, collecting white powder after freeze-drying, and annealing 5h at 900 ℃ to prepare the SnO2/C nanocomposite;
4) The material was etched 24 h with 3M NaOH solution at 80 ℃ to remove SiO2, and then the sample was neutralized with deionized water to adjust pH.
The concentration and the dosage of the medicine for reaction degradation are as follows: 10-4 mol/L80 mL methylene blue solution, 25 mg SnO2/C nanocomposite.
In this example, under ultraviolet light and visible light conditions, the photocatalytic reaction degradation rate of the SnO2/C nanocomposite on methylene blue is better than that of SnO2 synthesized by SnCl4 and two different tin sources of commercial SnO2 under the condition of using tetraisopropyl tin as a precursor (see fig. 1 a-b).
Claims (2)
1. Controllable hierarchical porous SnO 2 A method for preparing a photocatalyst, characterized in that the method comprises the following preparation processes:
1) Using tetraisopropyl tin as a tin source, and mixing glacial acetic acid and tetraisopropyl tin according to a volume ratio of 10:1, mixing; stirring glacial acetic acid and tetraisopropyl tin mixed solution at room temperature to form milky suspension, centrifuging to obtain white precipitate, and vacuum drying at 65deg.C to obtain SnO 2 Is a precursor of (2);
2) Mixing the sample prepared in the step 1) with 0.3 g sucrose and a certain amount of SiO with different particle sizes 2 Mixing the colloid solution and SnO 2 Precursor of (C), sucrose SiO 2 Adding 3 mL deionized water into the colloid mixed solution to dissolve the mixture, and uniformly mixing;
SiO in the step 2) 2 The size and the addition amount of the colloid are respectively as follows: the aperture is 0nm, and is not added; the pore diameter is 7 nm, the mass fraction is 30 wt%, and the addition amount is 1.1 g; the pore diameter is 12 nm, the mass fraction is 30 wt%, and the addition amount is 1.1 g; the pore diameter is 22 nm, the mass fraction is 40 wt%, and the addition amount is 0.75 g;
3) Rapidly freezing with liquid nitrogen, then freeze-drying 12-h, collecting white powder after freeze-drying, placing the composite material precursor in an inert atmosphere, and obtaining SnO under the annealing condition that the temperature is 500-1000 ℃ and the time is 1-7 h 2 C nanocomposite;
4)etching the above material with NaOH solution to remove SiO 2 Then washing with deionized water to neutrality;
5) Adding SnCl into control group 4 Synthetic SnO 2 And commercial SnO 2 Blank comparison is carried out as different tin sources, step 3 is repeated, and SnO without double templates under different precursor conditions is obtained 2 A nanomaterial.
2. A controlled graded porous SnO according to claim 1 2 The preparation method of the/C photocatalyst is characterized in that the tin source of the hollow white control precursor in the step 5) is SnCl 4 Commercial SnO 2 。
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| CN111545225A (en) * | 2020-04-17 | 2020-08-18 | 中国地质大学（北京） | Heterostructure photocatalyst for enhancing visible light response and preparation method thereof |
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