CN110911508A - Novel ultraviolet-visible all-band absorbing material and preparation method and application thereof - Google Patents
Novel ultraviolet-visible all-band absorbing material and preparation method and application thereof Download PDFInfo
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- 239000011358 absorbing material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 32
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 30
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 23
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011858 nanopowder Substances 0.000 claims abstract description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000005751 Copper oxide Substances 0.000 claims abstract description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 5
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 7
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 235000011837 pasties Nutrition 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims 1
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 claims 1
- 239000011368 organic material Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 3
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
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- 238000001514 detection method Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 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 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
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- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 metal oxide compound Chemical class 0.000 description 1
- 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 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
-
- 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
- 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
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- 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
-
- 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
Abstract
The invention discloses a novel ultraviolet-visible all-band absorbing material, a preparation method and application thereof, wherein the material comprises tin oxide, bismuth oxide, cadmium oxide, iron oxide, copper oxide and sulfur which are uniformly distributed in a composite material, and the molar ratio of each component is as follows: SnO2∶Bi2O3∶CdO∶Fe2O3CuO and S are a, b, c, d, e and f, wherein a is more than or equal to 2 and less than or equal to 3.5, b is more than or equal to 1.5 and less than or equal to 3, c is more than or equal to 1 and less than or equal to 2, and d is more than or equal to 0.5 and less than or equal to dE is more than or equal to 1, 0.5 and less than or equal to 0.8, and f is more than or equal to 0.5 and less than or equal to 0.8. The invention also provides a preparation method and application of the novel ultraviolet-visible all-band absorbing material. The nano powder material has high photoelectric conversion efficiency, wide sources of raw materials for preparation, low price and easy obtainment, simple preparation method and low cost; the nano powder is easy to be formed by tabletting, and meets the processing requirements of solar window materials.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and relates to a novel ultraviolet-visible all-band absorbing material, and a preparation method and application thereof.
Background
With the continuous development of human society, nonrenewable resources such as petroleum, coal, natural gas and the like are increasingly reduced, and meanwhile, the great use of the nonrenewable resources can cause great pollution to the environment, so that the development and research of alternative energy and renewable energy are extremely emphasized in various countries while the sustainable development of industries such as natural gas, petroleum, coal and the like is maintained. By 2025, photovoltaic power generation is expected to account for 6% -21% of the total power generation in countries around the world. In recent years, international photovoltaic power generation is developed very rapidly, developed countries such as the united states, europe and japan make a very huge and very delicate photovoltaic power generation development plan, the international photovoltaic market starts to develop from special applications, remote rural areas to the direction of combined power supply of building and grid-connected power generation, and meanwhile, photovoltaic power generation is also transited from supplementary energy to alternative energy.
A solar cell is also called a "solar chip" or a "photovoltaic cell", and is a photoelectric semiconductor sheet that directly generates electricity by using sunlight. It can output voltage and generate current under the condition of loop as long as it is illuminated by light meeting a certain illumination condition. Physically referred to as solar Photovoltaic (abbreviated PV), Photovoltaic for short. Solar cells are devices that directly convert light energy into electrical energy by the photoelectric or photochemical effect. Crystalline silicon solar cells working with the photoelectric effect are the mainstream, while thin film solar cells working with the photochemical effect are still in the germination stage. The window layer material has an important function in the solar cell, and in the prior art, the solar cell window material has the problems of complex preparation process, high energy consumption, serious pollution, low photoelectric conversion efficiency and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method and application of a sulfur-containing metal oxide compound multi-junction solar cell material which is cheap and easy to obtain, has higher photoelectric conversion efficiency, low production cost, no toxicity, no pollution, convenient processing, and renewable utilization, and can fully respond to the ultraviolet-visible light full-wave band (200 + 800nm), and the full absorption of ultraviolet-visible sunlight is realized by utilizing the regulation and control of a high-concentration surfactant on the microstructure of a semiconductor metal oxide (sulfide) compound so as to obtain a high-efficiency solar photoelectric conversion material and a photocatalyst for efficiently treating industrial sewage.
The organic matter containing the color group is decomposed and mineralized into non-toxic and harmless micromolecular substances by utilizing the obtained nano powder material under the radiation of sunlight; the solar window material with different thicknesses and areas can be directly made after tabletting, and the photovoltaic conversion can be directly carried out on sunlight, and the photovoltaic conversion efficiency is higher.
The invention is characterized in that the surface active agent cetyl trimethyl ammonium chloride is taken as a template, and the room temperature solid phase synthesis method is adopted to prepare the SnO with the energy gap gradient and the sulfur2/Bi2O3/CdO/Fe2O3The material has energy gap widths of △ E respectivelyg1.40-1.94 eV, and is an N-type multijunction semiconductor material.
The technical scheme is as follows:
a novel ultraviolet-visible full-waveband absorbing material comprises tin oxide, bismuth oxide, cadmium oxide, iron oxide, copper oxide and sulfur which are uniformly distributed in a composite material, wherein the molar ratio of each component is as follows: SnO2∶Bi2O3∶CdO∶Fe2O3CuO and S are a, b, c, d, e and f, wherein a is more than or equal to 2 and less than or equal to 3.5, b is more than or equal to 1.5 and less than or equal to 3, c is more than or equal to 1 and less than or equal to 2, d is more than or equal to 0.5 and less than or equal to 1, e is more than or equal to 0.5 and less than or equal to 0.8, and f is more than or equal to 0.5 and less than.
Further, SnO2∶Bi2O3∶CdO∶Fe2O3CuO, S, (a: b: c: d: e: f), (3.5-2.5), (2.5-1.5), (1.5-2), (0.7-1), (0.6-0.8) and (0.6-0.8); wherein the valence states of Sn, Bi, Cd, Fe and Cu are +4, +3, +2 and +2 respectively; the valency of the sulphur is mainly +4 and + 6.
Further, the SnO2、Bi2O3、CdO、Fe2O3And the crystallite size of CuO is in the range of5-15nm, and the particle size is 20-50 nm.
The invention relates to a preparation method of a novel ultraviolet-visible all-band absorbing material, which comprises the following steps:
(Me＝Sn4+，Bi3+，Cd2+，Fe3+，Cu2+，x≤3，1≤n≤4，x≤n，y≤1)。
step 1, weighing stannic chloride (SnCl) according to a certain molar ratio4.5H2O), bismuth nitrate (Bi (NO)3)3.5H2O), cadmium chloride (CdCl)2.2.5H2O), ferric chloride hexahydrate (FeCl)3.6H2O), copper chloride (CuCl)2.2H2O), sodium thiosulfate (Na)2S2O3.5H2O) and sodium hydroxide (NaOH), and the dosage of the template agent Cetyl Trimethyl Ammonium Chloride (CTAC) is weighed as 5-10% of the total mass of the reactants;
step 2, mixing and grinding the eight substances weighed in the step 1 in a mortar for 10-20 min to fully mix and react reactants to obtain brown pasty substances, standing for 1h, adding deionized water for soaking and stirring;
step 3, performing suction filtration and washing until no chloride ion exists in the filtrate (performing qualitative detection by using a silver nitrate solution);
step 4, drying the filter cake obtained in the step 3 at the temperature of 110-2/Bi2O3/CdO/Fe2O3Sulfur-containing multijunction metal oxide composite solar window materials of the combination/CuO (N/P/N/N/P).
The novel ultraviolet-visible full-waveband absorbing material is applied to the process of photocatalytic degradation of organic matters.
Further, the novel ultraviolet-visible full-waveband absorbing material is further ground and crushed, transferred into a photocatalytic reactor, added with organic sewage (such as methyl orange, methylene blue, a surfactant, a drug and the like) and subjected to light reaction at normal temperature and normal pressure.
Furthermore, the dosage ratio of the nano powder material to the sewage is 1: 1000g/L, the illumination wavelength is 365-800nm, and the illumination time is 30-60 min.
Compared with the prior art, the invention has the beneficial effects that:
the nano powder material can be recycled for 5 times or more by degrading organic matters in a neutral (pH is 6.0-7.5) environment, and the photocatalytic performance of the nano powder material is almost unchanged; but the stability of the photocatalyst gradually becomes worse in an acidic (pH 6 or less) environment.
The nano powder material has high photoelectric conversion efficiency, wide sources of raw materials for preparation, low price and easy obtainment, simple preparation method and low cost; the nano powder is easy to be formed by tabletting, and meets the processing requirements of solar window materials.
Drawings
FIG. 1 is a graph of the UV-VIS diffuse reflectance absorption spectrum of a sample.
Detailed Description
The technical solutions of the present invention will be described in further detail with reference to the accompanying drawings and the detailed description.
An ultraviolet-visible full-waveband absorption solar nano material comprises tin oxide, bismuth oxide, cadmium oxide, iron oxide, copper oxide and sulfur which are uniformly distributed in a composite material, wherein the molar ratio of each component is as follows: SnO2∶Bi2O3∶CdO∶Fe2O3CuO and S are a, b, c, d, e and f, wherein a is more than or equal to 2 and less than or equal to 3.5, b is more than or equal to 1.5 and less than or equal to 3, c is more than or equal to 1 and less than or equal to 2, d is more than or equal to 0.5 and less than or equal to 1, e is more than or equal to 0.5 and less than or equal to 0.8, and f is more than or equal to 0.5 and less than; the sulfur-modified tin oxide, bismuth oxide, cadmium oxide, iron oxide and copper oxide composite material absorbs ultraviolet light and visible light in sunlight to a certain degree (as shown in figure 1), and the doping of a proper amount of S can improve the light absorption intensity of the multi-element metal oxide and expand the light response range, so that a base material is provided for efficient utilization of solar energy.
SnO2∶Bi2O3∶CdO∶Fe2O3CuO, S, (a: b: c: d: e: f), (3.5-2.5), (2.5-1.5), (1.5-2), (0.7-1), (0.6-0.8) and (0.6-0.8); wherein the valence states of Sn, Bi, Cd, Fe and Cu are +4, +3, +2 and +2 respectively; the valency of the sulphur is mainly +4 and + 6. Sulfur enters the crystal lattice of each metal oxide to varying degrees.
The SnO2、Bi2O3、CdO、Fe2O3And the crystallite size of CuO is between 5 and 15nm, and the particle size is between 20 and 50 nm.
The preparation method of the ultraviolet-visible all-band absorption sheet comprises the following steps: respectively weighing stannic chloride (SnCl) according to a certain molar ratio4.5H2O), bismuth nitrate (Bi (NO)3)3.5H2O), cadmium chloride (CdCl)2.2.5H2O), ferric chloride hexahydrate (FeCl)3.6H2O), copper chloride (CuCl)2.2H2O), sodium thiosulfate (Na)2S2O3.5H2O) and sodium hydroxide (NaOH), and the dosage of the template agent of the hexadecyl trimethyl ammonium chloride is weighed to be 5-10% of the total mass of the reactants. Mixing and grinding the eight substances in a mortar for 10-20 min to fully mix and react reactants to obtain brown pasty substances, standing for 1h, adding deionized water for soaking and stirring, and then performing suction filtration and washing until filtrate contains no chloride ions (using silver nitrate solution for qualitative detection). Drying the obtained filter cake at the temperature of 110-DEG C and 120-DEG C, then moving the filter cake into a crucible, roasting the filter cake for 5 hours at the temperature of 450-DEG C and 500-DEG C in a muffle furnace, naturally cooling the filter cake to the room temperature, and then taking the filter cake out to obtain S @ SnO2/Bi2O3/CdO/Fe2O3Sulfur-containing multijunction metal oxide composite solar window materials of the combination/CuO (N/P/N/N/P). The absorption spectrum of the material is measured within the wavelength range of 200-800nm, and the material has full-spectrum absorption capacity of ultraviolet-visible light. The powder material is pressed into 0.5X 2cm slices under the pressure of 8MPa, and the photoelectric conversion efficiency is measured, and the maximum value can reach 27.64%. The application of the organic compound in the decomposition of organic matters has remarkable effect: under the radiation of sunlight, the organic matter is decomposed almost completely within 30-60 min.
Using surfactant Cetyl Trimethyl Ammonium Chloride (CTAC) as template, and tin chloride (SnCl)4.5H2O), bismuth nitrate (Bi (NO)3)3.5H2O), cadmium chloride (CdCl)2.2.5H2O), ferric chloride (FeCl)3.6H2O), copper chloride (CuCl)2.2H2O), sodium thiosulfate (Na)2S2O3.5H2O) and sodium hydroxide (NaOH) are used as precursors prepared from the nano powder material, under the premise of determined grinding time of 20min, standing time of 60min, drying temperature of 105 ℃ and roasting temperature of 460 ℃, under the process condition of determined matching of template agent dosage and different reaction precursors, the photoelectric conversion efficiency of the obtained nano powder material and the degradation liquid dosage ratio of the same nano powder dosage and organic pollutants are 1g/L, the initial concentration of the degradation liquid is 50mg/L, the photodegradation time is 60min, and the photocatalytic performance is shown in tables 1-3:
TABLE 1
TABLE 2
TABLE 3
Five metal oxides SnO in ultraviolet-visible full-waveband absorbing sheet material2，Bi2O3，CdO，Fe2O3Band gap Width (E) of CuOg) 3.5, 2.8, 2.5, 2.1 and 1.7eV respectively, and has energy gap gradient; the polymetal is modified by sulfurEnergy gap width of oxide Delta Eg1.4-1.94 eV. The composite crystal material constructs an internal potential electric field, is beneficial to energy coupling and accelerated separation of carriers excited by sunlight with different wavelengths, reduces the combination of carriers with different energy, improves the photoelectric conversion efficiency, and has mound advantages. The particle size of the nano composite powder material is closely related to the tunnel effect and the size effect of the nano particles, and the crystallite size, the photocatalytic efficiency and the photoelectric conversion efficiency are in positive correlation. The defect concentration in the crystal is beneficial to the interface polarization field generated by the transfer of charges and the separation of photon-generated carriers, but the stability of the photoelectric property is poor; under the accelerated separation of different internal electric fields, the migration rate of photoelectrons is improved, and the photoelectric conversion efficiency is improved.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (7)
1. A novel ultraviolet-visible all-band absorbing material is characterized by comprising tin oxide, bismuth oxide, cadmium oxide, iron oxide, copper oxide and sulfur which are uniformly distributed in a composite material, wherein the molar ratio of each component is as follows: SnO2∶Bi2O3∶CdO∶Fe2O3CuO and S are a, b, c, d, e and f, wherein a is more than or equal to 2 and less than or equal to 3.5, b is more than or equal to 1.5 and less than or equal to 3, c is more than or equal to 1 and less than or equal to 2, d is more than or equal to 0.5 and less than or equal to 1, e is more than or equal to 0.5 and less than or equal to 0.8, and f is more than or equal to 0.5 and less than.
2. The novel UV-visible all band absorber material of claim 1, wherein SnO2∶Bi2O3∶CdO∶Fe2O3CuO, S, (a: b: c: d: e: f), (3.5-2.5), (2.5-1.5), (1.5-2), (0.7-1), (0.6-0.8) and (0.6-0.8); wherein the valence states of Sn, Bi, Cd, Fe and Cu are +4, +3, +2 and +2 respectively; the valency of the sulphur is mainly +4 and + 6.
3. The novel uv-vis absorbing material in all bands as claimed in claim 1, wherein said SnO is selected from the group consisting of2、Bi2O3、CdO、Fe2O3And the crystallite size of CuO is between 5 and 15nm, and the particle size is between 20 and 50 nm.
4. A novel ultraviolet-visible all band absorbing material of claim 1, characterized in that,
the method comprises the following steps:
step 1, respectively weighing stannic chloride SnCl according to a certain molar ratio4.5H2O, bismuth nitrate Bi (NO)3)3.5H2O, cadmium chloride CdCl2.2.5H2FeCl, iron chloride hexahydrate3.6H2O, copper chloride CuCl2.2H2O, sodium thiosulfate Na282O3.5H2The amount of seven reactants of O and NaOH, and the amount of the template agent of hexadecyl trimethyl ammonium chloride is weighed as 5 to 10 percent of the total mass of the reactants;
step 2, mixing and grinding the eight substances weighed in the step 1 in a mortar for 10-20 min to fully mix and react reactants to obtain brown pasty substances, standing for 1h, adding deionized water for soaking and stirring;
step 3, carrying out suction filtration and washing until no chloride ion exists in the filtrate;
step 4, drying the filter cake obtained in the step 3 at the temperature of 110-2/Bi2O3/CdO/Fe2O3A sulfur-containing multijunction metal oxide composite solar window material of a CuO combination.
5. The use of the novel uv-vis full-band absorber material of claim 1 in photocatalytic degradation of organic materials.
6. The application of claim 5, wherein the novel ultraviolet-visible full-waveband absorbing material is further ground and crushed, transferred into a photocatalytic reactor, added with organic sewage, and subjected to light reaction at normal temperature and normal pressure.
7. The use as claimed in claim 6, wherein the ratio of the nano-powder material to the sewage is 1: 1000g/L, the illumination wavelength is 365-800nm, and the illumination time is 30-60 min.
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