CN110694645B - Indium zinc sulfide nanosheet/tubular tin oxide heterojunction, preparation method thereof and application thereof in degradation and removal of water pollutants - Google Patents
Indium zinc sulfide nanosheet/tubular tin oxide heterojunction, preparation method thereof and application thereof in degradation and removal of water pollutants Download PDFInfo
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- CN110694645B CN110694645B CN201911032719.2A CN201911032719A CN110694645B CN 110694645 B CN110694645 B CN 110694645B CN 201911032719 A CN201911032719 A CN 201911032719A CN 110694645 B CN110694645 B CN 110694645B
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 69
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 59
- 239000002135 nanosheet Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000015556 catabolic process Effects 0.000 title claims description 24
- 238000006731 degradation reaction Methods 0.000 title claims description 24
- 239000003403 water pollutant Substances 0.000 title abstract description 8
- 239000002071 nanotube Substances 0.000 claims abstract description 18
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical group [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 33
- 239000002131 composite material Substances 0.000 claims description 19
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000002121 nanofiber Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000002471 indium Chemical class 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical group [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 230000000593 degrading effect Effects 0.000 abstract description 6
- 229910052976 metal sulfide Inorganic materials 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 229910001432 tin ion Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- 229910006707 SnO2-2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical group [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses an indium zinc sulfide nanosheet/tubular tin oxide heterojunction and a preparation method thereof and application thereof in degrading and removing water pollutants; the tin oxide nanotube is prepared by an electrostatic spinning technology and a high-temperature calcination technology, and indium zinc sulfide nanosheets are uniformly grown on the surface of the tin oxide nanotube by using tin oxide as a substrate through oil bath, so that an indium zinc sulfide nanosheet/tubular tin oxide heterojunction is constructed. The indium zinc sulfide is an important metal sulfide, the band gap width of the indium zinc sulfide is 2.6-2.7eV, the indium zinc sulfide is a good semiconductor material, the prepared indium zinc sulfide nanosheet/tubular tin oxide heterojunction has a large specific surface area, more adsorption sites and catalytic active sites can be provided, the separation efficiency of photoproduction electrons and holes is effectively improved, the activity of a photocatalytic reaction is further improved, and the indium zinc sulfide is better used for separating and degrading photocatalytic water pollutants.
Description
Technical Field
The invention relates to the technical field of inorganic nano composite materials, in particular to preparation of an indium zinc sulfide nanosheet/tubular tin oxide heterojunction and photocatalytic degradation removal of water pollutants by the heterojunction.
Background
Environmental and energy problems are prominent in the 21 st century and various approaches have been tried to solve these two major problems. Among them, solar energy is the current popular research for treating environmental pollution. Hexavalent chromium is a common heavy metal pollutant, mainly from factory wastewater. Hexavalent chromium has high toxicity and bioaccumulation properties that can cause unpredictable damage to the human body and the environment. Unlike other common heavy metals (such as cadmium), chromium is present in solution in two forms: trivalent chromium and hexavalent chromium. Among them, the former is one of trace elements required by organisms, and its toxicity is much less than that of the latter. Thus, certain processes have been used to reduce hexavalent chromiumTrivalent chromium is an effective method for repairing polluted water. The photocatalysis technology is an efficient green method for solving the problems of environment and energy because of the advantages of mild conditions, high efficiency, low energy consumption and the like, and the core of the photocatalysis technology is a photocatalysis material. With the development of nanomaterials and nanotechnology, indium zinc sulfide (Znln)2S4) The nano photocatalytic material is favored by researchers, however, the nano indium zinc sulfide still has some problems in practical application, such as too fast photoproduction electron-hole recombination rate and low light quantum yield; easy to agglomerate, greatly reduces the photocatalytic activity and the like.
Disclosure of Invention
The invention aims to provide a preparation method of an indium zinc sulfide nanosheet/tubular nano tin heterojunction. Tin ions are uniformly adsorbed on PVP/SnCl by adopting a simple sol-gel electrostatic spinning technology2The surface of the fiber. Then, the membrane obtained by spinning is calcined at high temperature, the organic component PVP is burnt off, SnCl2Oxidized to tin oxide. By the two technologies, not only can a hollow tubular tin oxide structure be obtained, but also the subsequent Znln is facilitated2S4Nanosheet in SnO2And (4) growing the surface. In the invention, SnO2As a substrate, Znln is grown in an oil bath2S4Indium zinc sulfide nanosheets/tubular tin oxide heterojunctions are constructed by the nanosheets. Znln2S4As an important metal sulfide, the metal sulfide has a band gap width of 2.6-2.7eV, is a typical narrow band gap structure, and can directly absorb and utilize visible light. Compared with the traditional two-dimensional structure, Znln2S4The nano-sheets are uniformly fixed on the tubular SnO2On the nanotube, the exposed area is increased to the maximum extent, more catalytic active sites are provided, and therefore the separation efficiency of photo-generated electrons and holes is effectively improved, and the material is a photocatalytic material with good development prospect.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
the preparation method of the indium zinc sulfide nanosheet/tubular tin oxide heterojunction comprises the following steps:
(1) PVP and tin salt are used as raw materials, and an electrostatic spinning method is adopted to prepare the composite nanofiber;
(2) preparing SnO by calcining the composite nano-fiber obtained in the step (1) at high temperature2A nanotube;
(3) adding zinc salt, indium salt and sulfide into the solution, and then adding SnO2And (4) nanotube reaction to obtain indium zinc sulfide nanosheet/tubular tin oxide heterojunction.
A method for degrading and removing organic pollutants in water comprises the following steps:
(1) PVP and tin salt are used as raw materials, and an electrostatic spinning method is adopted to prepare the composite nanofiber;
(2) preparing SnO by calcining the composite nano-fiber obtained in the step (1) at high temperature2A nanotube;
(3) adding zinc salt, indium salt and sulfide into the solution, and then adding SnO2Nanotube, reacting to obtain indium zinc sulfide nanosheet/tubular tin oxide heterojunction;
(4) and placing the indium zinc sulfide nanosheet/tubular tin oxide heterojunction in water containing pollutants to realize degradation and removal of the pollutants in the water.
In the above technical scheme, the tin salt is SnCl2(ii) a The zinc salt, the indium salt and the sulfide are respectively zinc chloride, indium chloride and thioacetamide; the contaminant is a hexavalent chromium compound.
In the technical scheme, in the step (1), tin salt is added into a mixed solvent, then PVP is added to obtain a spinning solution, and then electrostatic spinning is carried out to prepare the composite nanofiber; the mixed solvent is N, N '-dimethylformamide and absolute ethyl alcohol, and the volume ratio of the N, N' -dimethylformamide to the absolute ethyl alcohol is preferably 1: 1; in the spinning solution, the concentration of the tin salt is 0.1g/mL, and the mass of PVP is 1-1.5 times, preferably 1.2 times of that of the tin salt. The invention adopts a simple sol-gel electrostatic spinning technology to uniformly adsorb tin ions on the composite nanofiber membrane, thereby not only obtaining a hollow tubular structure, but also being beneficial to uniform growth of indium zinc sulfide nanosheets on the surface of tubular tin oxide.
In the technical scheme, in the step (2), during high-temperature calcination, the heating rate is 1.5-3 ℃/min, and the preference is given2 ℃/min; the temperature is 500-650 ℃, preferably 600 ℃; after calcining and sintering, naturally cooling to room temperature to obtain SnO2A nanotube.
In the technical scheme, in the step (3), the molar ratio of the zinc salt to the indium salt to the sulfide is 1: 2: 4, and the zinc salt to the indium salt are sequentially used as a zinc source, an indium source and a sulfur source. During reaction, the pH is 2-3, preferably 2.5; the reaction temperature is 70-85 ℃, and preferably 80 ℃; the reaction time is 1.5-3 h, preferably 2 h. For example, zinc sulfide, indium sulfide and thioacetamide are sequentially added into a solution with pH of 2.5, ultrasonic treatment is carried out for 5 minutes, and then SnO is added2The nanotube is reacted; and after the reaction is finished, taking out the reaction product naturally cooled to room temperature, sequentially washing with water and ethanol, and then drying in a drying oven in vacuum to obtain the indium zinc sulfide nanosheet/tubular tin oxide heterojunction.
In the technical scheme, in the step (4), the degradation and removal of the pollutants in the water are carried out under illumination, and the illumination is visible illumination.
The invention further discloses application of the indium zinc sulfide nanosheet/tubular tin oxide heterojunction in degradation treatment of pollutants in water, and preferably the pollutants are hexavalent chromium compounds.
THE ADVANTAGES OF THE PRESENT INVENTION
1. In the preparation method of the indium zinc sulfide nanosheet/tubular tin oxide heterojunction, the electrostatic spinning technology is simple to operate, and tin ions can be uniformly distributed on the nanofiber membrane in the preparation process. The prepared nano-wire has smaller size, and the hollow tubular structure can be obtained by calcining. The hollow tubular tin oxide has larger specific surface area, can expose more active sites, enables more indium zinc sulfide nanosheets to grow, and is beneficial to the photocatalytic reaction.
2. Indium zinc sulfide is an important metal sulfide, the band gap width is 2.6-2.7eV, and the typical narrow band gap structure of the indium zinc sulfide enables the indium zinc sulfide to directly absorb and utilize visible light.
3. The invention takes tubular tin oxide as a substrate, and grows indium zinc sulfide nanosheets in an oil bath, thereby constructing an indium zinc sulfide nanosheet/tubular tin oxide heterojunction. The composite material has a large specific surface area, provides more adsorption sites and catalytic active sites, can effectively improve the separation efficiency of photoproduction electrons and holes, further improves the activity of photocatalytic reaction, and is better used for separating and degrading photocatalytic water pollutants.
Drawings
FIG. 1 is a scanning electron micrograph of an indium zinc sulfide nanosheet/tubular tin oxide heterojunction;
FIG. 2 is a transmission electron micrograph of an indium zinc sulfide nanosheet/tubular tin oxide heterojunction;
FIG. 3 is a graph showing the degradation of hexavalent chromium by indium zinc sulfide nanosheet/tubular tin oxide heterojunction;
FIG. 4 is a graph of the degradation profile of a zinc indium sulfide nanosheet/tubular tin oxide heterojunction with hexavalent chromium solutions of different initial concentrations;
fig. 5 is a graph of the degradation profile of indium zinc sulfide nanosheet/tubular tin oxide heterojunction for hexavalent chromium solutions of different initial pH.
Detailed Description
In order to solve the defects existing in the practical application of the nano photocatalytic material, the invention constructs the indium zinc sulfide nanosheet/tubular tin oxide heterojunction photocatalytic composite material by utilizing the methods of a sol-gel electrostatic spinning technology, a high-temperature calcination technology, an oil bath and the like, and the indium zinc sulfide serving as a semiconductor material can directly absorb and utilize visible light, has a narrow band gap structure and is novel tin oxide (SnO)2) The nano tube has more active sites, can be self-assembled with indium zinc sulfide, is a good carrier material, and has excellent technical effect when being used for degrading hexavalent chromium serving as a water pollutant.
The preparation method of the indium zinc sulfide nanosheet/tubular tin oxide heterojunction comprises the following steps:
(1) PVP and tin salt are used as raw materials, and an electrostatic spinning method is adopted to prepare the composite nanofiber;
(2) preparing SnO by calcining the composite nano-fiber obtained in the step (1) at high temperature2A nanotube;
(3) adding zinc salt, indium salt and sulfide into the solution, and then adding SnO2And (4) nanotube reaction to obtain indium zinc sulfide nanosheet/tubular tin oxide heterojunction.
Example one
Using a pipette to sequentially pipette 5mL of absolute ethanol and 5mL of N, N' -dimethylformamide, magnetically stirring for 5min, and adding 1g of SnCl2Stirring for 5 minutes, adding 1.2g of PVP while stirring, and continuously stirring for 12 hours to form a uniform and transparent solution; subsequently, the clear solution was used for electrospinning. Wherein the precursor solution is injected with a syringe for 0.2 mm min-1Feeding at constant speed, connecting a direct current power supply to provide high voltage of 15 KV, and placing an aluminum foil at a position 15cm away from a needle point to collect SnCl2the/PVP composite fiber.
Adding the SnCl2the/PVP composite fiber is calcined at high temperature of 600 ℃ and at the temperature rise rate of 2 ℃/min (from room temperature to 600 ℃), the calcined fiber is naturally cooled to the room temperature after being calcined for 3 hours, and the calcined product is ground into powder by a mortar to obtain tubular SnO2Here is SnO2A nanotube.
1mol of zinc chloride, 2mol of indium chloride and 4mol of thioacetamide were added to 30mL of ultrapure water (pH = 2.5, hydrochloric acid adjustment) in this order and sonicated for 10 minutes, and then 100mg of SnO was added2Continuously performing ultrasonic treatment on the nanotube powder for 30 minutes to obtain uniform suspension; transferring the suspension into a 100ml single-neck flask, carrying out oil bath reaction at 80 ℃ for 2 hours, and naturally cooling to room temperature after the reaction is finished; washing the obtained solution with ultrapure water and ethanol for three times in sequence, and then placing the solution in a vacuum oven for 12 hours at 60 ℃ to finally obtain indium zinc sulfide nanosheet/tubular tin oxide (ZIS/SnO)2) A heterojunction of ZIS/SnO2-1. Adjusting the molar weight of zinc chloride, indium chloride and thioacetamide to be 0.5mol, 1mol and 2 mol; 1.5mol, 3mol and 6 mol; 2mol, 4mol and 8 mol; according to different stoichiometric ratios, the obtained products are respectively named as ZIS/SnO2-0.5、ZIS/SnO2-1.5 and ZIS/SnO2-2。
FIG. 1 is a scanning electron microscope image of the indium zinc sulfide nanosheet/tubular tin oxide, and FIG. 2 is a transmission electron microscope image of the indium zinc sulfide nanosheet/tubular tin oxide heterojunction. It can be seen from the above figures that the small-sized flake indium zinc sulfide grows uniformly on the surface of the tin oxide nanotubes.
Example two
The indium zinc sulfide nanosheet/tubular tin oxide heterojunction of the first embodiment is placed in simulated wastewater containing hexavalent chromium (a hexavalent chromium solution is obtained by using potassium dichromate as a chromium source), a xenon lamp is used as a light source, illumination is carried out for a certain time, and a change curve of the concentration of the hexavalent chromium in the water along with the illumination time is measured, so that the photocatalytic degradation effect of the composite material on pollutants in the water under visible light is evaluated.
And adding the prepared 30mg indium zinc sulfide nanosheet/tubular tin oxide heterojunction into 50mL hexavalent chromium sewage with the concentration of 50 ppm. Stirring for 1h in the dark to reach adsorption equilibrium. And then, turning on a xenon lamp light source, and carrying out visible light photocatalytic degradation on the hexavalent chromium in the water by using the catalyst.
The specific hexavalent chromium degradation effect is detected by an ultraviolet-visible spectrophotometer and calculated by a hexavalent chromium concentration-absorbance working curve. The method comprises the following specific steps: absorbing a certain amount of solution at certain time intervals, and filtering the catalyst by using a filter head to obtain hexavalent chromium solutions under different degradation times. And (3) measuring the absorbance of the hexavalent chromium solution by adding a color developing agent, and calculating the degradation efficiency by using an absorbance formula. Recording the initial concentration of the hexavalent chromium as 100%, and gradually reducing the concentration of the hexavalent chromium solution along with the progress of the photocatalytic process to obtain a hexavalent chromium degradation curve after finishing. FIG. 3 is a graph showing the degradation curve of the indium zinc sulfide nanosheet/tubular tin oxide heterojunction composite material to hexavalent chromium in water, and the first 60 minutes is the equilibrium adsorption time.
The method is adopted for comparison test:
when PVP is 2g in the first embodiment and the rest is unchanged, the obtained indium zinc sulfide nanosheet/tubular tin oxide heterojunction ZIS/SnO2-1 at 80 minutes, the hexavalent chromium degradation rate is 89%; when the titanium carbide/indium zinc sulfide composite visible-light-induced photocatalyst prepared in the first example of CN110124706A is used, the degradation rate of hexavalent chromium is 69% in 80 minutes.
EXAMPLE III
And (3) testing the degradation curve of the indium zinc sulfide nanosheet/tubular tin oxide heterojunction when the concentrations of the initial hexavalent chromium solutions are different. The test method of example two was used to test the efficiency of the degradation of hexavalent chromium at different initial concentrations, decreasing with increasing concentration. When the concentration is 10ppm, the degradation rate can reach 100% within 10 minutes, and the effect is very good. When the initial concentration is 20ppm and 30ppm, the initial concentration can reach 100 percent in 30 and 60 minutes respectively, which shows that the composite material is more favorable for the photocatalytic degradation of low-concentration hexavalent chromium. FIG. 4 is a degradation curve diagram of indium zinc sulfide nanosheet/tubular tin oxide heterojunction when the initial concentrations of hexavalent chromium solutions are different.
Indium zinc sulfide nanosheet/tubular tin oxide heterojunction (ZIS/SnO) when the pH of the initial hexavalent chromium solution (concentration 50 ppm) is different2-1) testing of the degradation curve. By adopting the step of the second embodiment, when the pH is slightly acidic, the degradation effect is good; when the pH value is alkaline, the degradation effect is poor, the conclusion is consistent with other documents, and the acidic condition is favorable for photocatalytic degradation of hexavalent chromium, and the alkaline condition is unfavorable for photocatalytic degradation of hexavalent chromium. FIG. 5 is a graph showing the degradation of a zinc indium sulfide nanosheet/tubular tin oxide heterojunction when the initial hexavalent chromium solution has a different pH.
The invention prepares the tin oxide nanotube by electrostatic spinning technology and high-temperature calcination technology. Tin oxide is used as a substrate, and indium zinc sulfide nanosheets uniformly grow on the surface of the tin oxide through oil bath, so that an indium zinc sulfide nanosheet/tubular tin oxide heterojunction is constructed. Indium zinc sulfide is an important metal sulfide, has a band gap width of 2.6-2.7eV, and is a good semiconductor material. The prepared indium zinc sulfide nanosheet/tubular tin oxide heterojunction has a large specific surface area, can provide more adsorption sites and catalytic active sites, effectively improves the separation efficiency of photoproduction electrons and holes, further improves the activity of photocatalytic reaction, and is better used for separating and degrading photocatalytic water pollutants.
Claims (10)
1. The indium zinc sulfide nanosheet/tubular tin oxide heterojunction is characterized in that the preparation method of the indium zinc sulfide nanosheet/tubular tin oxide heterojunction comprises the following steps:
(1) PVP and tin salt are used as raw materials, and an electrostatic spinning method is adopted to prepare the composite nanofiber;
(2) preparing SnO by calcining the composite nano-fiber obtained in the step (1) at high temperature2A nanotube;
(3) adding zinc salt, indium salt and sulfide into the solution, and then adding SnO2And (4) nanotube reaction to obtain indium zinc sulfide nanosheet/tubular tin oxide heterojunction.
2. Indium zinc sulfide nanosheet/tubular tin oxide heterojunction as claimed in claim 1 wherein the tin salt is SnCl2(ii) a The zinc salt, the indium salt and the sulfide are respectively zinc chloride, indium chloride and thioacetamide.
3. An indium zinc sulfide nanosheet/tubular tin oxide heterojunction as claimed in claim 1 wherein in step (1) a tin salt is added to the mixed solvent, followed by the addition of PVP to obtain a spinning solution, followed by electrospinning to produce the composite nanofibers.
4. Indium zinc sulfide nanosheet/tubular tin oxide heterojunction as claimed in claim 3 wherein the mixed solvent is N, N' -dimethylformamide and anhydrous ethanol; in the spinning solution, the concentration of the tin salt is 0.1g/mL, and the mass of PVP is 1-1.5 times of that of the tin salt.
5. An indium zinc sulfide nanosheet/tubular tin oxide heterojunction as claimed in claim 1 wherein in step (2), the temperature rise rate during high temperature calcination is 1.5-3 ℃/min and the temperature is 500-650 ℃.
6. Indium zinc sulfide nanosheets/tubular tin oxide heterojunction as claimed in claim 1 wherein in step (3) the molar ratio of zinc salt, indium salt, sulfide is 1: 2: 4.
7. An indium zinc sulfide nanosheet/tubular tin oxide heterojunction as claimed in claim 1 wherein in step (3), the pH is 2 to 3 during the reaction.
8. An indium zinc sulfide nanosheet/tubular tin oxide heterojunction as claimed in claim 1 wherein in step (3), the reaction temperature is from 70 to 85 ℃ and the reaction time is from 1.5 to 3 hours.
9. Use of an indium zinc sulfide nanosheet/tubular tin oxide heterojunction as claimed in claim 1 for the degradation removal of contaminants from water.
10. Use according to claim 9, characterized in that the contaminant is a hexavalent chromium compound.
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