CN102513134B - Compound photocatalysis material with bismuth sulfide nano particles/bismuth oxychloride and preparation method thereof - Google Patents
Compound photocatalysis material with bismuth sulfide nano particles/bismuth oxychloride and preparation method thereof Download PDFInfo
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- CN102513134B CN102513134B CN 201110344121 CN201110344121A CN102513134B CN 102513134 B CN102513134 B CN 102513134B CN 201110344121 CN201110344121 CN 201110344121 CN 201110344121 A CN201110344121 A CN 201110344121A CN 102513134 B CN102513134 B CN 102513134B
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Abstract
The invention relates to a compound photocatalysis material with bismuth-sulfide nano particles/bismuth oxychloride and a preparation method thereof. The preparation method comprises the following steps of: firstly, dissolving bismuth nitrate and chlorinated 1-dodecyl-3-methyl glyoxaline into ethylene glycol monomethyl ether respectively, afterwards carrying out a thermal reaction by a solvent soas to prepare bismuth-oxychloride micron balls, then adding the bismuth-oxychloride micron balls into a water solution containing a sulfur source and exchanging parts of ions so as to prepare a compound photocatalysis material containing bismuth-sulfide nano particles and bismuth oxychloride. The method disclosed by the invention can be executed at room temperature and normal pressure, the cost is low, and equipment is simple and is easy to operate; and moreover, the compound photocatalysis material with the bismuth-sulfide nano particles/bismuth oxychloride can be produced at a large scale and has important potential application in the aspect of industrial production. The prepared compound photocatalysis material with the bismuth sulfide/bismuth oxychloride has favorable absorption of visible light, the separation of a photon-generated carrier is obviously improved, and the photocatalysis performance of the material is greatly enhanced.
Description
Technical field
The present invention relates to a kind of novel visible light-responded bismuth sulfide nano particle/bismoclite composite photocatalyst material and preparation method thereof that has, belong to the preparing technical field of catalysis material.
Background technology
Semi-conductor nano particles is because physics, the chemical property of its a series of novelties have caused people's interest widely at power conversion, ultracapacitor and catalytic field.Wherein, the semi-conductor nano particles/quantum dot of narrow band gap has tangible quantum size effect, changes semi-conductive energy gap with the variation of particle size, and then absorbs sunshine fully.The semi-conductor nano particles of narrow band gap and the semiconductor of broad-band gap (as titanium dioxide) is compound, utilize the quantum size effect of narrow gap semiconductor can make composite effectively absorb visible light, and the electric charge that is conducive between the interface shifts, thereby has good application prospects.
As a kind of binary semiconductor of layer structure, bismuth sulfide has important use at aspects such as photovoltaic, thermoelectricity and electrochemical hydrogen storages.In recent years, because the bismuth sulfide band gap has narrower band gap (1.3eV), the quantum size effect of its nano particle makes bismuth sulfide have adjustable photoactivate and photocatalysis property in the visible region.Yet, the general higher reaction temperature of needs of the method for preparing the bismuth sulfide nano particle of present report, and need chelating agent to stablize the nano particle of bismuth sulfide, this has just increased the complexity of preparation process.A kind of preparation method of flower-shaped or rod-shaped bismuth sulfide nanomaterial is disclosed as patent CN101468813A.This method is reaction dissolvent with 1-cetyl-3-methyl imidazolium tetrafluoroborate, is presoma with dialkyl dithiophosphoric acid bismuth salt, under agitation is heated to 135-250 ℃ of reaction and just can makes.From angle of practical application, develop the nano particle that a kind of simple liquid phase approach prepares bismuth sulfide and be very important.
Summary of the invention
The present invention is directed to traditional catalysis material light absorption difference and the high problem of carrier recombination rate, and the complicated problem of preparation bismuth sulfide nano particle method, a kind of bismuth sulfide nano particle/bismoclite composite photocatalyst material is provided, and this material has adjustable, the characteristics of high efficiency of visible absorption.A kind of method of simple this material of preparation is provided simultaneously, and this method is with low cost, is easy to large-scale production.Light absorption that can controlled material significantly improves the separation of photo-generated carrier, improves the photocatalysis performance of composite.
The technical scheme that the present invention takes is:
A kind of bismuth sulfide nano particle/bismoclite composite photocatalyst material, it is made up of bismuth sulfide nano particle and bismoclite, and bismuth sulfide mass percent in compound is 0.1%-5.75%.
The preparation method of a kind of bismuth sulfide nano particle/bismoclite composite photocatalyst material may further comprise the steps:
(1) the bismoclite micron ball of preparation graded structure: be dissolved in bismuth nitrate and chlorination 1-dodecyl-3-methylimidazole in the EGME respectively, magnetic agitation a period of time is dissolved it fully, then two kinds of solution are mixed and continue and stir, transfer in the enclosed autoclave at last, place 140-180 ℃ to react 2-12 hour down, to be cooled to room temperature, with product collection, washing, vacuum drying, obtain the bismoclite micron ball of graded structure;
(2) preparation bismuth sulfide/bismoclite composite: bismoclite micron ball is joined in the aqueous solution that contains the sulphur source, 0-60 ℃ of (preferred room temperature) lower magnetic force stirred 2-4 hour, sulphion and the bismoclite generation ion-exchange reactions that produces decomposed in the sulphur source, generate bismuth sulfide/bismoclite composite, described sulphur source is thiocarbamide, cysteine or thioacetamide.
The mol ratio of the described bismuth nitrate of step (1), chlorination 1-dodecyl-3-methylimidazole is 1: 1.5; Preferred 1: 507 of the mole dosage ratio of bismuth nitrate and EGME.
The mol ratio in the described bismoclite micron of step (2) ball, sulphur source is 1: 1; Preferred 1: 4444 of the mol ratio of sulphur source and water.
Method of the present invention can be implemented under the room temperature normal pressure, and cost is low, and equipment is simple to operation, and can be mass-produced, and has important potential application aspect industrial production.Bismuth sulfide/bismoclite the composite photocatalyst material of preparation has good visible absorption, has significantly improved the separation of photo-generated carrier, has improved material photocatalytic properties greatly.Find out that from the light absorption figure (Fig. 1) of material (400-750nm) has adjustable light absorption to bismuth sulfide nano particle/bismoclite composite in the visible region; By Photocatalytic Activity for Degradation 2, the performance of 4-chlorophenesic acid (Fig. 2) as can be seen, independent bismoclite or bismuth sulfide can degrade respectively under the radiation of visible light at 150 minutes 40.8% and 47.1% 2,4-chlorophenesic acid molecule, and the photocatalysis efficiency of bismuth sulfide nano particle/bismoclite composite reaches 82.3% under the similarity condition, and material of the present invention is than independent bismuth sulfide or independent bismoclite better effects if.
Description of drawings
Fig. 1 is the light absorption figure of bismuth sulfide nano particle of the present invention/bismoclite composite and contrast material, b wherein, c, d are respectively the bismuth sulfide nano particle/bismoclite composites for preparing as the sulphur source with thiocarbamide, cysteine, thioacetamide under the room temperature; E is at 60 ℃ of bismuth sulfide nano particle/bismoclite composites that obtain as the sulphur source with thioacetamide down of oil bath.
Fig. 2 is the Photocatalytic Activity for Degradation 2 of composite of the present invention and contrast material, 4-chlorophenesic acid performance comparison figure.
The specific embodiment
Further specify below in conjunction with this patent of embodiment.
Embodiment 1
0.97g bismuth nitrate and 0.86g chlorination 1-dodecyl-3-methylimidazole are dissolved in respectively in the 40mL EGME, and magnetic agitation dissolved it in 30 minutes fully.Then two kinds of solution are mixed and continue and stirred 10 minutes, transfer in the enclosed autoclave at last.Place 160 ℃ to react 2 hours down.To be cooled to room temperature, with product collection, washing, vacuum drying, obtain the bismoclite micron ball of graded structure.
(1) 0.261g bismoclite micron ball is joined in the aqueous solution that contains the 0.075g thioacetamide, the mol ratio of bismoclite and thioacetamide is 1: 1, the room temperature lower magnetic force stirred 2-4 hour, thioacetamide decomposes sulphion and the bismoclite generation ion-exchange reactions that produces, and generates bismuth sulfide/bismoclite composite.
Embodiment 2
(1) 0.97g bismuth nitrate and 0.86g chlorination 1-dodecyl-3-methylimidazole are dissolved in respectively in the 40mL EGME, magnetic agitation dissolved it in 30 minutes fully.Then two kinds of solution are mixed and continue and stirred 10 minutes, transfer in the enclosed autoclave at last.Place 160 ℃ to react 2 hours down.To be cooled to room temperature, with product collection, washing, vacuum drying, obtain the bismoclite micron ball of graded structure.
(2) 0.261g bismoclite micron ball is joined in the aqueous solution that contains the 0.076g thiocarbamide, the mol ratio of bismoclite and thiocarbamide is 1: 1, the room temperature lower magnetic force stirred 2-4 hour, thiocarbamide decomposes sulphion and the bismoclite generation ion-exchange reactions that produces, and generates bismuth sulfide/bismoclite composite.
Embodiment 3
(1) 0.97g bismuth nitrate and 0.86g chlorination 1-dodecyl-3-methylimidazole are dissolved in respectively in the 40mL EGME, magnetic agitation dissolved it in 30 minutes fully.Then two kinds of solution are mixed and continue and stirred 10 minutes, transfer in the enclosed autoclave at last.Place 160 ℃ to react 2 hours down.To be cooled to room temperature, with product collection, washing, vacuum drying, obtain the bismoclite micron ball of graded structure.
(2) 0.261g bismoclite micron ball is joined in the aqueous solution that contains the 0.121g cysteine, the mol ratio of bismoclite and cysteine is 1: 1, the room temperature lower magnetic force stirred 2-4 hour, cysteine decomposes sulphion and the bismoclite generation ion-exchange reactions that produces, and generates bismuth sulfide/bismoclite composite.
Embodiment 4
(1) 0.97g bismuth nitrate and 0.86g chlorination 1-dodecyl-3-methylimidazole are dissolved in respectively in the 40mL EGME, magnetic agitation dissolved it in 30 minutes fully.Then two kinds of solution are mixed and continue and stirred 10 minutes, transfer in the enclosed autoclave at last.Place 160 ℃ to react 2 hours down.To be cooled to room temperature, with product collection, washing, vacuum drying, obtain the bismoclite micron ball of graded structure.
(2) 0.261g bismoclite micron ball is joined in the aqueous solution that contains the 0.075g thioacetamide, the mol ratio of bismoclite and thioacetamide is 1: 1, in oil bath 60 ℃ magnetic agitation 2-4 hour, thioacetamide decomposes sulphion and the bismoclite generation ion-exchange reactions that produces, and generates bismuth sulfide/bismoclite composite.
Light absorption and visible light photocatalysis performance test:
Light absorption is with the sample compressing tablet, and optically pure barium sulfate is as the back of the body end, in ultraviolet-visible spectrophotometer (Tianjin, island UV2550 instrument) mensuration, this apparatus preparation integrating sphere.The test result of the product of embodiment 1-4 is seen accompanying drawing 1.
The visible light photocatalysis performance is to carry out photocatalytic degradation with 2,4-chlorophenesic acid as pollutant to characterize.Quantity of sample (100 milligrams) is distributed to certain density 2, in the 4-chlorophenesic acid solution, places dark place magnetic agitation to make it reach the adsorption/desorption balance in one hour.Open the xenon lamp (ultraviolet light being filtered with filter plate) of 300W then, take out the suspension of five milliliters of effects at set intervals with dropper.Treat to get its supernatant in quartz colorimetric utensil after centrifugal, analyze pollutant 2 in ultraviolet-visible spectrophotometer, the absorbance of 4-chlorophenesic acid changes, thereby characterizes its degradation effect.
Claims (3)
1. the preparation method of bismuth sulfide nano particle/bismoclite composite photocatalyst material is characterized in that, may further comprise the steps:
(1) the bismoclite micron ball of preparation graded structure: be dissolved in bismuth nitrate and chlorination 1-dodecyl-3-methylimidazole in the EGME respectively, magnetic agitation a period of time is dissolved it fully, then two kinds of solution are mixed and continue and stir, transfer in the enclosed autoclave at last, place 140-180 ℃ to react 2-12 hour down, to be cooled to room temperature, with product collection, washing, vacuum drying, obtain the bismoclite micron ball of graded structure;
(2) preparation bismuth sulfide/bismoclite composite: bismoclite micron ball is joined in the aqueous solution that contains the sulphur source, and the mol ratio in bismoclite micron ball, sulphur source is 1:1; 0-60 ℃ of temperature lower magnetic force stirs, and sulphion and the bismoclite generation ion-exchange reactions that produces decomposed in the sulphur source, generates bismuth sulfide/bismoclite composite, and described sulphur source is thiocarbamide, cysteine or thioacetamide.
2. the preparation method of bismuth sulfide nano particle according to claim 1/bismoclite composite photocatalyst material is characterized in that, the mol ratio of the described bismuth nitrate of step (1), chlorination 1-dodecyl-3-methylimidazole is 1:1.5.
3. the preparation method of bismuth sulfide nano particle according to claim 1/bismoclite composite photocatalyst material is characterized in that, the described temperature of step (2) is room temperature, magnetic agitation 2-4 hour.
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| CN106540750B (en) * | 2016-10-21 | 2019-01-29 | 山东大学 | With visible light-responded small numerator modified catalysis material and preparation method |
| CN106693994A (en) * | 2016-12-14 | 2017-05-24 | 中南大学 | Preparation and application of core-shell structure bismuth sulfide@copper sulfide composite microspheres |
| CN106694050B (en) * | 2016-12-29 | 2019-06-28 | 上海应用技术大学 | A kind of preparation method of kernel-shell structure, visible light catalyst |
| CN107983371B (en) * | 2017-11-21 | 2020-06-02 | 山东大学 | Photocatalytic material Cu2-xS/Mn0.5Cd0.5S/MoS2And preparation method and application thereof |
| CN107999095B (en) * | 2017-12-20 | 2020-03-24 | 河南师范大学 | Preparation method of sulfur-doped bismuth oxychloride powder photocatalytic material |
| CN109529035B (en) * | 2018-12-18 | 2021-03-05 | 新乡医学院 | Preparation method of near-infrared light-enriched cysteine-modified bismuth sulfide hollow sphere and application of bismuth sulfide hollow sphere in photothermal therapy and drug controlled release |
| CN110282658A (en) * | 2019-08-02 | 2019-09-27 | 湖南柿竹园有色金属有限责任公司 | A kind of high-purity bismuth sulfide preparation method |
| CN112246259A (en) * | 2020-11-19 | 2021-01-22 | 长春大学 | Bismuth telluride sensitized bismuth oxychloride nano composite material and preparation method and application thereof |
| CN116253546A (en) * | 2022-12-30 | 2023-06-13 | 广东原创新材料科技有限公司 | Photodynamic antibacterial inorganic product and preparation method and application thereof |
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