CN102513133B - Preparation method of flower ball-shaped micro-nano film photocatalytic material - Google Patents
Preparation method of flower ball-shaped micro-nano film photocatalytic material Download PDFInfo
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- CN102513133B CN102513133B CN201110342416.8A CN201110342416A CN102513133B CN 102513133 B CN102513133 B CN 102513133B CN 201110342416 A CN201110342416 A CN 201110342416A CN 102513133 B CN102513133 B CN 102513133B
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Abstract
The invention which relates to a preparation method of a flower ball-shaped micro-nano film photocatalytic material belongs to the technical field of environment chemical engineering photocatalytic water processing. The method which adopts a process combining alcoholysis with coating and allows a BiOCl film to be prepared on a titanium plate matrix comprises the following steps: 1, treating BiCl3 as a raw material and an alcohol as a solvent, adjusting the pH value by ammonia water, and reacting for 1-2h at 40-80DEG C to prepare a liquid precursor; and 2, coating the liquid precursor on the titanium plate matrix, drying, and washing to prepare the flower ball-shaped micro-nano film photocatalytic material having the diameter of 1-2mum and formed by flower balls assembled by nanosheets. The method has the advantages of simple preparation technology, mild condition, short operation period, and convenient realization of batch production, and the prepared film which has a unique space morphology and a good photocatalytic activity can be applied to the photocatalystic degradation of organic pollutants in water or air.
Description
Technical field
The preparation method of a kind of flower ball-shaped micro-nano film photocatalytic material of the present invention, is specifically related to a kind of preparation method and application of flower ball-shaped micro-nano BiOCl film photocatalytic material, belongs to environmental chemical engineering photocatalysis technology field.
Background technology
Recently, chlorine oxygen bismuth (BiOCl), as a kind of conductor photocatalysis material that has good photocatalytic activity, is subject to showing great attention to of researchers, in the photocatalysis treatment field of organic pollution, has vast potential for future development.Conventionally researcher mainly adopts Hydrolyze method or solvent-thermal method to prepare sheet or microspheroidal BiOCl fine catalyst.Tsing-Hua University adopts NaBiO
3transform Hydrolyze method and prepared the serial powder photocatalyst of BiOX (X=Cl, Br, I), and take PCP-Na as target degradation product, investigated catalytic activity (the Catalysis Communications of three kinds of photochemical catalysts under xenon lamp, 2010,11:460-464; Catalysis Communications, 2009,10:1957-1961).Institutes Of Technology Of Taiyuan utilizes BiCl
3and BiBr
3for adopting Hydrolyze method, raw material made BiOCl and BiOCl/BiOBr composite photo-catalyst (CN101879455A; CN102068998A).Shanghai second Industry Univ adopts BiCl
35H
2o be raw material take ethylene glycol as solvent, adopt solvent-thermal method prepared microspheroidal BiOC powder (CrystEngComm, 2010,12:3791-3796).East China University of Science is with Bi (NO
3)
35H
2o and CTAC are respectively He Lv source, bismuth source, adopt solvent-thermal method containing having prepared microspheroidal BiOCl powder (Journal of Photochemistry and Photobiology A:Chemistry 215 (2010) 76-80) in teflon-lined stainless steel cauldron.Also there is researcher to adopt physical vapour deposition (PVD) and chemical oxidization method to prepare BiOCl film (CN101724839A).The existing preparation method overwhelming majority is the preparation of research fine catalyst, fine catalyst has the features such as specific surface is large, reaction rate is high, easily make, but there is the fatal shortcomings such as dispersiveness is not good, difficult separation with solution, difficulty recovery, particularly for the fine particle with micro-nano structure; And catalyst immobilization is made to the film of micro-nano structure, not only retained the miniature scale of catalyst, more be conducive to Separation of Solid and Liquid and recycling, and be not only confined to process organic pollutants, and can expand to processing airborne organic pollution.
Summary of the invention
The preparation method's of a kind of flower ball-shaped micro-nano film photocatalytic material of the present invention object is to provide a kind of process for fixation of chlorine oxygen bismuth photochemical catalyst, prepare a kind of flower ball-shaped micro-nano BiOCl film photocatalytic material, overcome the shortcoming of the difficult recycling of Powdered photochemical catalyst, and be applied in water in organic processing.The method is take bismuth trichloride as raw material, alcohol is solvent, ammoniacal liquor is pH value conditioning agent, prepare precursor liquid, then precursor liquid is coated on matrix, drying, washing operation have been prepared flower ball-shaped micro-nano BiOCl film under normal temperature and pressure, realized the immobilization of small catalyst granules and retained its large specific area, therefore improved organic ability in Treatment by Photocatalysis Oxidation water.Raw materials usedly commonly be easy to get, reaction condition without HTHP, simple to operate, safely, be easy to realize suitability for industrialized production.Institute's made membrane, in the research of degradation water organic matter, is had to good photocatalytic activity under ultraviolet light, and film performance is stable, reusable.
The preparation method of a kind of flower ball-shaped micro-nano film photocatalytic material of the present invention, it is characterized in that take bismuth trichloride as raw material, alcohol is solvent, ammoniacal liquor is pH value conditioning agent, adopt alcoholysis method to prepare precursor liquid, then precursor liquid is coated on titanium board substrate, drying, washing make flower ball-shaped micro-nano BiOCl film photocatalytic material, and concrete steps are as follows:
I, take 0.2～1 gram analyze pure BiCl
3be positioned in 10～50mL alcoholic solvent, be heated to 40～80 ℃, stir and make its dissolving;
Ammoniacal liquor regulator solution pH value to 7～9 of II, employing 25%～28%, react 1～2 hour, make white emulsion, are precursor liquid;
III, the precursor liquid making in Step II is coated on the titanium board substrate that surface cleaning is clean, be positioned over afterwards in 75～80 ℃ of baking ovens and dry, and then apply, dry 5～30 times, finally be positioned in 75～80 ℃ of baking ovens and dry again 2～3h, taking-up is cleaned with distilled water immersion, making by diameter is 1～2 μ m, flower ball-shaped (as shown in Figure 2) the micro-nano BiOCl film (as shown in Figure 1) that the bouquet that nanometer sheet assembles forms, this film photocatalytic material is applied in water in organic Treatment by Photocatalysis Oxidation, particularly in water, trace toxic is harmful in the processing of hardly degraded organic substance, light source used is wavelength 365nm ultraviolet light, reaction condition is: normal temperature and pressure, made BiOCl film photocatalytic material is positioned in aqueous organopolysiloxane just to light source, from reactor bottom, blast air.
The preparation method of above-mentioned a kind of flower ball-shaped micro-nano BiOCl film photocatalytic material, is characterized in that described alcoholic solvent is ethylene glycol or ethanol or propane diols.
The preparation method's of a kind of flower ball-shaped micro-nano film photocatalytic material of the present invention advantage is:
1) realized the immobilization of micro-nano size BiOCl, facilitated the recycling of Separation of Solid and Liquid and catalyst, and the degraded that is both conveniently applied to organic pollutants is also conveniently applied to the degraded of organic pollution in air;
2) reaction condition gentleness, without using HTHP and special reactor, adopts simple method can make flower ball-shaped micro-nano BiOCl film photocatalytic material;
3) made BiOCl film photocatalytic material has the space structure of flower ball-shaped Nano/micron, and specific area is larger;
4) made BiOCl film photocatalytic material has good and stable photocatalytic activity (as shown in Figure 3) under ultraviolet light, and has the longer life-span;
5) made BiOCl film photocatalytic material is conveniently realized additional small electrical field control, thereby can realize the method degradable organic pollutant that adopts photoelectrocatalysis.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the flower ball-shaped Nano/micron BiOCl film photocatalytic material prepared of embodiment of the present invention 1.
Fig. 2 is the SEM figure of the flower ball-shaped Nano/micron BiOCl film photocatalytic material prepared of embodiment of the present invention 1.
Fig. 3 is the UV-Vis DRS collection of illustrative plates of the flower ball-shaped Nano/micron BiOCl film photocatalytic material prepared of embodiment of the present invention 1.
The specific embodiment
In order to make technical scheme of the present invention clearer, will specifically describe in detail with embodiment below, but content of the present invention is not confined to the scope of cited embodiment.
Embodiment 1
1) take 0.2 gram and analyze pure BiCl
3be positioned in 10mL ethylene glycol, be heated to 60 ℃, stir and make its dissolving;
2) the ammoniacal liquor regulator solution pH value to 9 of employing 25%-28%, reacts 1 hour, makes white emulsion, is precursor liquid;
3) by step 2) in the precursor liquid that makes be coated on the titanium board substrate that surface cleaning is clean, be positioned over afterwards in 80 ℃ of baking ovens and dry, and then repetitive coatings, oven dry 30 times, finally be positioned in 80 ℃ of baking ovens and dry again 3h, taking-up is cleaned with distilled water immersion, makes flower ball-shaped micro-nano BiOCl film photocatalytic material.
Institute's made membrane is used for to photocatalytic degradation water methyl orange, reaction condition is: normal temperature and pressure, the methyl orange aqueous solution 50mL of 10mg/L, get the made membrane 1cm × 6cm of institute as photochemical catalyst, from reactor bottom, blast air, at interval of certain hour sample analysis, with UV-VIS spectrophotometry, measure the conversion ratio of methyl orange.Under ultraviolet light, in 150min, to the degradation rate of methyl orange, can approach 100%, reuse after 4 times, in 150min, the degradation rate of methyl orange is still greater than to 90%.
Embodiment 2
1) take 0.4 gram and analyze pure BiCl
3be positioned in 20mL ethylene glycol, be heated to 80 ℃, stir and make its dissolving;
2) the ammoniacal liquor regulator solution pH value to 7 of employing 25%-28%, reacts 1.5 hours, makes white emulsion, is precursor liquid;
3) by step 2) in the precursor liquid that makes be coated on the titanium board substrate that surface cleaning is clean, be positioned over afterwards in 75 ℃ of baking ovens and dry, and then repetitive coatings, oven dry 15 times, finally be positioned in 75 ℃ of baking ovens and dry again 3h, taking-up is cleaned with distilled water immersion, makes flower ball-shaped micro-nano BiOCl film photocatalytic material.
Institute's made membrane is used for to photocatalytic degradation water methyl orange, reaction condition is: normal temperature and pressure, the methyl orange aqueous solution 50mL of 10mg/L, get the made membrane 1cm × 6cm of institute as photochemical catalyst, from reactor bottom, blast air, at interval of certain hour sample analysis, with UV-VIS spectrophotometry, measure the conversion ratio of methyl orange.Under ultraviolet light, in 150min, to the degradation rate of methyl orange, can reach 95%, reuse after 4 times, in 150min, the degradation rate of methyl orange is still greater than to 90%.
Embodiment 3
1) take 0.8 gram and analyze pure BiCl
3be positioned in 40mL propane diols, be heated to 80 ℃, stir and make its dissolving.
2) adopt ammoniacal liquor regulator solution pH value to 7, react 2 hours, make white emulsion.
3) by step 2) in the emulsion brushing that makes to the clean matrix of surface cleaning, brush 25 times, after each brushing, be put in 80 ℃ of baking ovens and dry and continue again brushing.After precursor liquid is all coated on matrix, then dry 2.5h, soaking and washing, makes flower ball-shaped micro-nano BiOCl film photocatalytic material.
Institute's made membrane is used for to photocatalytic degradation water methyl orange, reaction condition is: normal temperature and pressure, the methyl orange aqueous solution 50mL of 10mg/L, get the made membrane 1cm × 6cm of institute as photochemical catalyst, from reactor bottom, blast air, at interval of certain hour sample analysis, with UV-VIS spectrophotometry, measure the conversion ratio of methyl orange.Under ultraviolet light, in 150min, to the degradation rate of methyl orange, can reach more than 95%, reuse 3 degradation rates and still can reach 90%.
Embodiment 4
1) take 1 gram and analyze pure BiCl
3be positioned in 50mL ethanol, be heated to 40 ℃, stir and make its dissolving;
2) the ammoniacal liquor regulator solution pH value to 9 of employing 25%-28%, reacts 1.5 hours, makes white emulsion, is precursor liquid;
3) by step 2) in the precursor liquid that makes be coated on the titanium board substrate that surface cleaning is clean, be positioned over afterwards in 80 ℃ of baking ovens and dry, and then repetitive coatings, oven dry 15 times, finally be positioned in 80 ℃ of baking ovens and dry again 3h, taking-up is cleaned with distilled water immersion, makes flower ball-shaped micro-nano BiOCl film photocatalytic material.
Institute's made membrane is used for to photocatalytic degradation water methyl orange, reaction condition is: normal temperature and pressure, the methyl orange aqueous solution 50mL of 10mg/L, get the made membrane 1cm × 6cm of institute as photochemical catalyst, from reactor bottom, blast air, at interval of certain hour sample analysis, with UV-VIS spectrophotometry, measure the conversion ratio of methyl orange.Under ultraviolet light, in 150min, to the degradation rate of methyl orange, can reach 95%, reuse after 3 times, in 150min, the degradation rate of methyl orange is still greater than to 90%.
Claims (2)
1. the preparation method of a flower ball-shaped micro-nano film photocatalytic material, it is characterized in that take bismuth trichloride as raw material, alcohol is solvent, ammoniacal liquor is pH value conditioning agent, adopt alcoholysis method to prepare precursor liquid, then precursor liquid is coated on titanium board substrate, drying, washing make flower ball-shaped micro-nano BiOCl film photocatalytic material, and concrete steps are as follows:
2. according to the preparation method of a kind of flower ball-shaped micro-nano film photocatalytic material claimed in claim 1, it is characterized in that described alcoholic solvent is ethylene glycol, ethanol or propane diols.
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| CN102744087B (en) * | 2012-08-22 | 2014-01-15 | 太原理工大学 | Electrochemistry preparation method for flaky nanometer bismuth oxychloride film photocatalyst |
| CN103537303B (en) * | 2013-09-24 | 2015-04-15 | 合肥工业大学 | High-performance micro-nano multi-level structure BiOCl photocatalytic material and preparation method thereof |
| CN104525226B (en) * | 2014-12-25 | 2016-08-24 | 太原理工大学 | A kind of photocatalyst Bi4o5br2synthesis and application process |
| CN105251515A (en) * | 2015-10-25 | 2016-01-20 | 复旦大学 | Visible-light-driven photocatalyst Ag-AgCl-BiOCl and preparation method and application thereof |
| CN108499580A (en) * | 2017-02-23 | 2018-09-07 | 南开大学 | A method of poor iodine-type BiOI photocatalysis films are prepared by solvent-thermal method |
| CN113546523B (en) * | 2021-07-23 | 2023-03-31 | 上海师范大学 | PVDF ultrafiltration membrane of composite Ag @ BiOBr photocatalytic material and preparation method and application thereof |
| JP7395064B1 (en) | 2022-12-15 | 2023-12-08 | 三菱電機株式会社 | Photocatalyst carrier and method for producing photocatalyst carrier |
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| US6365007B1 (en) * | 1997-10-01 | 2002-04-02 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Photocatalysts for the degradation of organic pollutants |
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| US6365007B1 (en) * | 1997-10-01 | 2002-04-02 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Photocatalysts for the degradation of organic pollutants |
Non-Patent Citations (4)
| Title |
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| TiO2光催化薄膜的制备及其性能;李国兰等;《山西化工》;20010215;第21卷(第1期);全文 * |
| 李国兰等.TiO2光催化薄膜的制备及其性能.《山西化工》.2001,第21卷(第1期),全文. |
| 涂覆法制备TiO2薄膜光电极及催化性能研究;郭向丹等;《太原理工大学学报》;20021120;第33卷(第6期);全文 * |
| 郭向丹等.涂覆法制备TiO2薄膜光电极及催化性能研究.《太原理工大学学报》.2002,第33卷(第6期),全文. |
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