CN103007971A - Zinc tungstate/bismuth oxyiodide heterojunction visible light photocatalysis material and fabrication method thereof - Google Patents
Zinc tungstate/bismuth oxyiodide heterojunction visible light photocatalysis material and fabrication method thereof Download PDFInfo
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- CN103007971A CN103007971A CN2012105676717A CN201210567671A CN103007971A CN 103007971 A CN103007971 A CN 103007971A CN 2012105676717 A CN2012105676717 A CN 2012105676717A CN 201210567671 A CN201210567671 A CN 201210567671A CN 103007971 A CN103007971 A CN 103007971A
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Abstract
The invention belongs to the field of new materials, and relates to a zinc tungstate/bismuth oxyiodide heterojunction visible light photocatalysis material and a fabrication method thereof. The photocatalysis material comprises zinc tungstate and bismuth oxyiodide, wherein the mol ratio of bismuth oxyiodide is 25%-50%. The fabrication method comprises the steps of dissolving zinc acetate and sodium wolframate in deionized water, adding a sodium tungstate solution into a zinc acetate solution to obtain a zinc tungstate nanorod, dissolving potassium iodide in the deionized water, adding bismuth nitrate, adding the prepared zinc tungstate nanorod into a mixed solution, and finally obtaining the zinc tungstate/bismuth oxyiodide heterojunction photocatalysis material. The method can be conducted at room temperature and under normal pressure, is low in cost, simple in process, and suitable for large-scale production, and has important potential application in industrial production. The prepared zinc tungstate/bismuth oxyiodide heterojunction photocatalysis material can better response to visible light, and shows an excellent visible light photocatalysis performance.
Description
Technical field
The invention belongs to field of new, relate to a kind of Zinc Tungstate/bismuth oxyiodide hetero-junctions visible-light photocatalysis material and preparation method thereof.
Background technology
In recent years, photocatalysis is obtaining general concern aspect environmental improvement and the energy development, and the research and development of catalysis material are just becoming at present the focus of research both at home and abroad.Yet the practical application of photochemical catalyst is subject to the restriction of two factors: the photo-generated carrier recombination probability is high and spectral response range is narrow.Therefore, the visible-light photocatalysis material of seeking to have high-efficiency catalytic activity will be that photocatalysis technology further moves towards practical inexorable trend.
Zinc Tungstate is showing good photocatalytic activity as a kind of important photochemical catalyst aspect photodissociation water and the degradable organic pollutant.Zhu Yongfa seminar of Tsing-Hua University has reported on 46, the 8372-8378 with hydro-thermal method and has synthesized nanometer Zinc Tungstate photochemical catalyst that this photochemical catalyst shows stronger ultraviolet light photocatalysis in the process of rhodamine B degradation solution active at Inorg.Chem.2007.But because Zinc Tungstate has larger band-gap energy, only under the irradiation of ultraviolet light, just can be excited, and be subjected to light induced electron hole that optical excitation produces to the compound shortcoming such as fast, limit its application in practice.In order to take full advantage of sunshine, Zinc Tungstate is carried out modification, make its spectral absorption expand to visible region and improve its visible light photocatalysis active, significant for the practical value of exploitation Zinc Tungstate photochemical catalyst.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, poor and the high problem of carrier recombination probability for the light absorption of Zinc Tungstate material, provide a kind of based on Zinc Tungstate Zinc Tungstate, efficient/bismuth oxyiodide hetero-junctions visible-light photocatalysis material, a kind of method of simple this material of preparation is provided simultaneously, the method is with low cost, be easy to large-scale production, can significantly improve the separation probability of photo-generated carrier, improve the photocatalysis performance of material.
The present invention is achieved in the following ways:
Zinc Tungstate/bismuth oxyiodide hetero-junctions visible-light photocatalysis material is characterized in that it is made of Zinc Tungstate and bismuth oxyiodide, and chemical formula is ZnWO
4/ BiOI, the mol ratio of bismuth oxyiodide is 25%～50% in the component.
The preparation method of above-mentioned Zinc Tungstate/bismuth oxyiodide hetero-junctions visible-light photocatalysis material is characterized in that may further comprise the steps:
(1) preparation Zinc Tungstate nanometer rods: zinc acetate and sodium tungstate are dissolved in respectively in the deionized water, then join sodium tungstate solution in the acetic acid zinc solution and stir, with the pH value of ammonia spirit regulator solution; After stirring mixed solution is transferred in the reactor, is placed 180 ℃ of lower reactions 12 hours, naturally cool to room temperature after, with products therefrom collection, washing, drying, obtain the Zinc Tungstate nanometer rods;
(2) preparation Zinc Tungstate/bismuth oxyiodide heterojunction photocatalysis material: KI is dissolved in the deionized water, adds the bismuth nitrate of Isoequivalent weight and continue stirring; Then add the Zinc Tungstate nanometer rods that step (1) makes in above-mentioned mixed solution, stirring at room is even, follows 80 ℃ of heating water baths 2 hours; With products therefrom collection, washing, drying, obtain Zinc Tungstate/bismuth oxyiodide heterojunction photocatalysis material.
The preparation method of above-mentioned Zinc Tungstate/bismuth oxyiodide hetero-junctions visible-light photocatalysis material is characterized in that the consumption mol ratio of the described zinc acetate of step (1), sodium tungstate is 1:1.The consumption mol ratio of the described Zinc Tungstate nanometer rods of step (2), KI is 1:0.33～1.
It is a kind of effective ways that improve the material visible-light photocatalytic activity that two or more different semi-conducting materials are compounded to form hetero-junctions.Hetero-junctions utilizes built in field so that carrier transport has directionality, can improve the separation probability of photo-generated carrier, in addition that narrow gap semiconductor and wide band gap semiconducter is compound, can expand the response spectrum scope of wide band gap semiconducter by the sensibilization of narrow gap semiconductor.Bismuth oxyiodide is as a kind of novel semi-conductor catalysis material, and its band-gap energy is 1.73-1.92eV, can effectively absorb visible light.And bismuth oxyiodide can be compounded to form Zinc Tungstate/bismuth oxyiodide heterojunction structure with N-shaped semiconductor Zinc Tungstate as a kind of p-type semiconductor, is expected to obtain having the heterojunction photocatalyst of efficient visible light photocatalytic activity.
Method of the present invention can be carried out under the room temperature normal pressure, and with low cost, technique is simple, is suitable for large-scale production, has important potential application aspect industrial production.The Zinc Tungstate of preparation/bismuth oxyiodide heterojunction photocatalysis material is responding to visible light well, show excellent visible light photocatalysis performance, greater than the radiation of visible light of 420nm after 4 hours, the efficient of Zinc Tungstate/bismuth oxyiodide heterojunction photocatalysis material degraded methyl orange reaches 86% at wavelength.By contrast, pure Zinc Tungstate does not almost show the visible light catalytic ability, and the degradation efficiency of pure bismuth oxyiodide only has 26%.
The specific embodiment
The below provides three most preferred embodiments of the present invention.
Embodiment 1
(1) 0.219g zinc acetate and 0.330g sodium tungstate are dissolved in respectively in the 10ml deionized water, stirred 10 minutes, then sodium tungstate solution is dropwise joined in the acetic acid zinc solution and continue and stir, with the pH value to 9.0 of the 25wt%-28wt% ammonia spirit regulator solution that dilutes.Stir and after 20 minutes mixed solution transferred in the reactor of 25ml, place 180 ℃ of lower reactions 12 hours, naturally cool to room temperature after, with products therefrom collection, washing, drying, obtain the Zinc Tungstate nanometer rods.
(2) the 0.166g KI is dissolved in the 20ml deionized water, adds the 0.485g bismuth nitrate and continue and stir.Then add 0.314g Zinc Tungstate nanometer rods in above-mentioned mixed solution, the mol ratio of KI and Zinc Tungstate is 1:1, and stirring at room 0.5 hour is followed 80 ℃ of heating water baths 2 hours.With products therefrom collection, washing, drying, obtain Zinc Tungstate/bismuth oxyiodide heterojunction photocatalysis material, made catalyst called after ZB-1.The mol ratio of bismuth oxyiodide is 50% in the component.
Greater than the radiation of visible light of 420nm after 4 hours, the efficient of Zinc Tungstate/bismuth oxyiodide heterojunction photocatalysis material degraded methyl orange reaches 75% at wavelength.
Embodiment 2
(1) 0.219g zinc acetate and 0.330g sodium tungstate are dissolved in respectively in the 10ml deionized water, stirred 10 minutes, then sodium tungstate solution is dropwise joined in the acetic acid zinc solution and continue and stir, with the pH value to 9.0 of the 25wt%-28wt% ammonia spirit regulator solution that dilutes.Stir and after 20 minutes mixed solution transferred in the reactor of 25ml, place 180 ℃ of lower reactions 12 hours, naturally cool to room temperature after, with products therefrom collection, washing, drying, obtain the Zinc Tungstate nanometer rods.
(2) the 0.083g KI is dissolved in the 20ml deionized water, adds the 0.243g bismuth nitrate and continue and stir.Then add 0.314g Zinc Tungstate nanometer rods in above-mentioned mixed solution, the mol ratio of KI and Zinc Tungstate is 1:2, and stirring at room 0.5 hour is followed 80 ℃ of heating water baths 2 hours.With products therefrom collection, washing, drying, obtain Zinc Tungstate/bismuth oxyiodide heterojunction photocatalysis material, made catalyst called after ZB-2.The mol ratio of bismuth oxyiodide is 33% in the component.
Greater than the radiation of visible light of 420nm after 4 hours, the efficient of Zinc Tungstate/bismuth oxyiodide heterojunction photocatalysis material degraded methyl orange reaches 86% at wavelength.
Embodiment 3
(1) 0.219g zinc acetate and 0.330g sodium tungstate are dissolved in respectively in the 10ml deionized water, stirred 10 minutes, then sodium tungstate solution is dropwise joined in the acetic acid zinc solution and continue and stir, with the pH value to 9.0 of the 25wt%-28wt% ammonia spirit regulator solution that dilutes.Stir and after 20 minutes mixed solution transferred in the reactor of 25ml, place 180 ℃ of lower reactions 12 hours, naturally cool to room temperature after, with products therefrom collection, washing, drying, obtain the Zinc Tungstate nanometer rods.
(2) the 0.055g KI is dissolved in the 20ml deionized water, adds the 0.162g bismuth nitrate and continue and stir.Then add 0.314g Zinc Tungstate nanometer rods in above-mentioned mixed solution, the mol ratio of KI and Zinc Tungstate is 1:3, and stirring at room 0.5 hour is followed 80 ℃ of heating water baths 2 hours.With products therefrom collection, washing, drying, obtain Zinc Tungstate/bismuth oxyiodide heterojunction photocatalysis material, made catalyst called after ZB-3.The mol ratio of bismuth oxyiodide is 25% in the component.
Greater than the radiation of visible light of 420nm after 4 hours, the efficient of Zinc Tungstate/bismuth oxyiodide heterojunction photocatalysis material degraded methyl orange reaches 50% at wavelength.
Claims (4)
1. Zinc Tungstate/bismuth oxyiodide hetero-junctions visible-light photocatalysis material is characterized in that being made of Zinc Tungstate and bismuth oxyiodide, and the mol ratio of bismuth oxyiodide is 25%～50% in the component.
2. the preparation method of described Zinc Tungstate/bismuth oxyiodide hetero-junctions visible-light photocatalysis material according to claim 1 is characterized in that may further comprise the steps:
(1) preparation Zinc Tungstate nanometer rods: zinc acetate and sodium tungstate are dissolved in respectively in the deionized water, then sodium tungstate solution are joined in the acetic acid zinc solution and stirring, with the pH value to 9.0 of ammonia spirit regulator solution; After stirring the mixed solution of sodium tungstate and zinc acetate is transferred in the reactor, placed 180 ℃ of lower reactions 12 hours, naturally cool to again room temperature, with products therefrom collection, washing, drying, obtain the Zinc Tungstate nanometer rods;
(2) KI is dissolved in the deionized water, adds bismuth nitrate and the stirring of Isoequivalent weight; Then add the Zinc Tungstate nanometer rods that step (1) makes in the mixed solution of above-mentioned KI and bismuth nitrate, stirring at room was even, with 80 ℃ of heating water baths 2 hours; With products therefrom collection, washing, drying, obtain Zinc Tungstate/bismuth oxyiodide heterojunction photocatalysis material.
3. the preparation method of Zinc Tungstate according to claim 2/bismuth oxyiodide hetero-junctions visible-light photocatalysis material is characterized in that the consumption mol ratio of zinc acetate, sodium tungstate in the step (1) is 1:1.
4. the preparation method of Zinc Tungstate according to claim 2/bismuth oxyiodide hetero-junctions visible-light photocatalysis material is characterized in that the consumption mol ratio of Zinc Tungstate nanometer rods, KI in the step (2) is 1:0.33～1.
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| CN103846085A (en) * | 2014-03-17 | 2014-06-11 | 湖州师范学院 | Hydrothermal method for preparing Bi-doped ZnWO4 photocatalyst |
| CN103920508A (en) * | 2014-03-28 | 2014-07-16 | 山东大学 | Nitrated carbon fiber loaded bismuth oxyhalide nanoflower and preparation method of nanoflower |
| CN104437550A (en) * | 2014-11-25 | 2015-03-25 | 上海交通大学 | Method for preparing zinc tungstate-cadmium sulfide heterojunction photocatalyst |
| CN105214695A (en) * | 2015-11-17 | 2016-01-06 | 中国科学院海洋研究所 | A kind of Bi 2wO 6/ BiOI heterojunction composite photocatalyst and its preparation method and application |
| CN105642316A (en) * | 2015-12-22 | 2016-06-08 | 江苏大学 | Method for preparing BiOI / CdWO4 heterojunction photocatalyst |
| CN107032299A (en) * | 2016-02-03 | 2017-08-11 | 天津大学 | Carry platinum wolframic acid zinc nano material and its application in air-sensitive field |
| CN111254461A (en) * | 2020-01-19 | 2020-06-09 | 安徽大学 | Tungsten oxide/bismuth oxyiodide heterojunction material for photo-reduction of carbon dioxide and preparation method and application thereof |
| CN112973671A (en) * | 2021-03-22 | 2021-06-18 | 合肥工业大学 | Nano bismuth tungstate/zinc oxide heterojunction catalyst, preparation method and application thereof |
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| CN103920508A (en) * | 2014-03-28 | 2014-07-16 | 山东大学 | Nitrated carbon fiber loaded bismuth oxyhalide nanoflower and preparation method of nanoflower |
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| CN105214695A (en) * | 2015-11-17 | 2016-01-06 | 中国科学院海洋研究所 | A kind of Bi 2wO 6/ BiOI heterojunction composite photocatalyst and its preparation method and application |
| CN105642316A (en) * | 2015-12-22 | 2016-06-08 | 江苏大学 | Method for preparing BiOI / CdWO4 heterojunction photocatalyst |
| CN107032299A (en) * | 2016-02-03 | 2017-08-11 | 天津大学 | Carry platinum wolframic acid zinc nano material and its application in air-sensitive field |
| CN107032299B (en) * | 2016-02-03 | 2019-03-08 | 天津大学 | Carry platinum wolframic acid zinc nano material and its application in air-sensitive field |
| CN111254461A (en) * | 2020-01-19 | 2020-06-09 | 安徽大学 | Tungsten oxide/bismuth oxyiodide heterojunction material for photo-reduction of carbon dioxide and preparation method and application thereof |
| CN111254461B (en) * | 2020-01-19 | 2021-08-27 | 安徽大学 | Tungsten oxide/bismuth oxyiodide heterojunction material for photo-reduction of carbon dioxide and preparation method and application thereof |
| CN112973671A (en) * | 2021-03-22 | 2021-06-18 | 合肥工业大学 | Nano bismuth tungstate/zinc oxide heterojunction catalyst, preparation method and application thereof |
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