CN103721713A - Three-phase composite visible-light-driven photocatalyst capable of efficiently degrading dyes - Google Patents
Three-phase composite visible-light-driven photocatalyst capable of efficiently degrading dyes Download PDFInfo
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
本发明公开了一种三相复合可见光催化剂及其制备方法和应用，属于材料制备及环境污染治理的技术领域。采用化学氧化法制备石墨烯，然后将石墨烯还原形成还原石墨烯，采用溶剂热法合成还原石墨烯/Bi2MoO6复合物，再采用浸渍-还原法将Au负载于复合物上，形成还原石墨烯/Bi2MoO6/Au三相复合物。本发明制备的光催化剂比表面积大，活性组分利用高，具有高效可见光光催化降解有机物的效果。The invention discloses a three-phase composite visible light catalyst and its preparation method and application, belonging to the technical field of material preparation and environmental pollution control. Graphene was prepared by chemical oxidation, then reduced to form reduced graphene, and reduced graphene/Bi 2 MoO 6 composite was synthesized by solvothermal method, and Au was loaded on the composite by impregnation-reduction method to form reduced Graphene/Bi 2 MoO 6 /Au three-phase composite. The photocatalyst prepared by the invention has large specific surface area, high utilization of active components, and has the effect of highly efficient visible light photocatalytic degradation of organic matter.
Description
Technical field
The technical field that the invention belongs to material preparation and environmental pollution improvement, is specifically related to three-phase composite visible light catalyst of a kind of efficient degradation dyestuff organic pollution and preparation method thereof.
Background technology
Along with the continuous discharge of industrial wastewater and the continuous uses of various dyestuffs such as dyestuff is synthetic, printing and dyeing, the dye quantity of entered environment and kind constantly increase, and the environmental pollution that dyestuff causes is on the rise.According to statistics, the dyestuff in the whole world about 15% is discharged in waste water in process of production, and these colorful wastewaters can generate poisonous accessory substance by oxidation, hydrolysis and other chemical reaction in environment.At present traditional pollution control means (physical treatment, biological treatment, conventional chemical processing) can not thoroughly be eliminated, and therefore develop a kind of green, free of contamination processing means are imperative.
Photocatalysis technology is a kind of high-level oxidation technology, and its principle is that photochemical catalyst is as titanium dioxide (TiO
2) under the effect of ultraviolet light, produce hole and electronics, and further by chemical action, produce some high activity groups such as thering are highly active various free radicals, participate in redox reaction degradation of contaminant.This technology has very strong mineralization ability to organic matter, thereby makes poisonous organic matter permineralization become inorganic matter or be converted into free of contamination product.At present, TiO
2the application of photocatalysis technology in environmental protection has relevant report.But, the TiO generally using
2there is the low and low drawback of solar energy utilization ratio of quantum efficiency in based photocatalyst.For these problems, researchers are to TiO
2carried out that a large amount of study on the modification comprises that various metals and nonmetal doping, precious metal surface deposition, semiconductor are compound, dye sensitization etc., make some progress, but fundamentally do not solve yet these two significant problems of quantum efficiency and solar energy utilization ratio, thereby impel researchers further sight line to be turned to non-TiO
2the compound of series, attempts the efficient photochemical catalyst of development of new and the response range of widening photochemical catalyst.
We have reported under radiation of visible light in previous work, the dyestuff organic matter of bismuth molybdate in can degradation water, but bismuth molybdate photochemical catalyst quantum efficiency is low, and light induced electron and hole easily compound, cause the photocatalysis performance of bismuth molybdate lower.For easily compound problem of catalyst photo-generated carrier, be generally to adopt catalyst to carry out modification, with this, suppress the compound of light induced electron hole.In numerous method of modifying, structure composite photo-catalyst has been proved to be to improve the effective way of catalyst photocatalysis degradation organic contaminant.In composite photo-catalyst, the interface between compound semiconductor light-catalyst or metal causes more effectively interface electronics to shift, thereby photo-generated carrier is effectively separated.So far, the bismuth molybdate base composite photocatalyst of having reported mainly contains Bi
2moO
6/ TiO
2, Bi
2moO
6/ C, Ag/AgBr/Bi
2moO
6, Graphene/Bi
2moO
6deng, all effectively improved the activity of bismuth molybdate photocatalysis degradation organic contaminant.Wherein, complexing agent Graphene is a kind of superior co-catalyst, it is a kind of nano material of the bi-dimensional cellular shape lattice structure being become by monolayer carbon atom close-packed arrays, because Graphene is the layer structure of graphite, there are in its surface a large amount of not paired electronics to move about, this makes the electric conductivity of the existing metal of Graphene have again semi-conductive performance, and CNT also has large specific area and is easy to adsorb organic compound, these factors all contribute in theory take electronics transmission as main interface light-catalyzed reaction, be conducive to the adding of Graphene to suppress right compound in light induced electron-hole, improve the photocatalytic activity of catalyst.Yu et al. has built Bi
2moO
6-RGO nano-complex, improved the bactericidal property of bismuth molybdate photochemical catalyst, but its activity still has much room for improvement, in recent years, research about three-phase composite photochemical catalyst shows, three-phase composite object light catalyst shows the catalytic activity higher than two-phase compound, traces it to its cause as three-phase composite photochemical catalyst can better suppress the compound of light induced electron hole, thereby greatly improves the performance of photochemical catalyst photocatalysis degradation organic contaminant.Numerous research shows, at catalyst surface loaded with nano gold grain, can effectively improve photocatalysis performance, and nanogold particle can serve as electric transmission track, thereby improves the right separation rate in light induced electron-hole of catalyst surface, and the activity of catalyst is improved greatly.Based on this, on the basis of Graphene/bismuth molybdate two-phase compound, further supported nano-gold particle forms three-phase composite thing, is used for degradation of dye organic pollution, and this has greater significance to promoting the application of bismuth molybdate in degradation of dye organic wastewater.
Summary of the invention
The object of the present invention is to provide three-phase composite visible light catalyst of a kind of efficient degradation dyestuff organic pollution and preparation method thereof.This photochemical catalyst specific area is large, and active component is utilized high, can realize the dyestuff organic pollution in efficient degradation waste water, has larger application potential.
For achieving the above object, the present invention adopts following technical scheme:
The present invention adopts solvent-thermal method and dipping-reducing process respectively reduced graphene and gold to be carried on to bismuth molybdate surface, and then the efficient visible light catalyst of synthetic reduced graphene/bismuth molybdate/golden three-phase composite, wherein reduced graphene and golden mass concentration are 0.1%-0.4%.
Described preparation method's concrete steps are: the preparation of (1) reduced graphene: take respectively 3 g graphite and 18 g potassium permanganate, after being ground, join formation suspension in the concentrated sulfuric acid (360ml) and phosphoric acid (40ml), suspension is incubated after 12 h at 50 ℃, be cooled to room temperature, be poured in 400 mL frozen water, after stirring, drip the H of 30wt.%
2o
2until be golden yellow, continue to be stirred to still after, centrifugal, taking precipitate, respectively with 10wt.%HCl solution and deionized water washing, until occur that colloid substance cannot be centrifugal.Take out colloid substance, by dialysis, make the ion concentration of sol solution be less than 5 ppm.Jelly is diluted to after desired concn by deionized water, utilizes ultrasonication that graphite oxide is peeled off, obtain graphene oxide.Get appropriate above-mentioned graphene oxide, add a certain amount of vitamin C (VC) solution, stir, it is incubated after 50 min at 95 ℃, obtain reduced graphene; (2) preparation of Graphene/bismuth molybdate two-phase compound: a certain amount of reduced graphene is joined respectively in polytetrafluoroethylene (PTFE) reactor, stir, splash into respectively Bi (NO
3)
35H
2o (0.27M) and Na
2moO
42H
2the ethylene glycol solution of O (0.13M), after 10 min, drip NaOH (10 M) solution, regulate pH value to be about 9, continue to stir after 30 min, take off reactor and put into stainless steel outer lining, in the baking oven of 160 ℃, react 3 h, question response still is cooled to after room temperature, and the mixture in liner is carried out to centrifugation, the precipitation of gained successively, with distilled water and absolute ethanol washing, is ground standby in baking oven after 80 ℃ of oven dry; (3) preparation of Graphene/bismuth molybdate/golden three-phase composite thing: take a certain amount of Graphene/bismuth molybdate compound of having prepared, put into beaker, add appropriate amount of deionized water, stir, splash into respectively different volumes chlorauric acid solution (10 mg/mL), stir one hour, under ultraviolet lamp, irradiate 4 h, centrifugal, dry, obtain Graphene/bismuth molybdate/golden three-phase composite compound.
Remarkable advantage of the present invention is:
(1) the present invention is carried on reduced graphene and gold on bismuth molybdate first, has effectively separated light induced electron and hole, is a kind of catalyst of novel visible response.
(2) visible light catalyst of reduced graphene/bismuth molybdate/golden three-phase composite is the organic pollution such as rhodamine B degradation efficiently.
Accompanying drawing explanation
Fig. 1 is the powder X-ray RD figure of the Graphene/bismuth molybdate/golden three-phase composite photochemical catalyst of embodiment 2,4,5 and 6 gained.
Fig. 2 is the powder TEM figure of the Graphene/bismuth molybdate/golden three-phase composite photochemical catalyst of embodiment 6 gained.
Fig. 3 is the design sketch of the Graphene/bismuth molybdate/golden three-phase composite photocatalyst for degrading rhodamine B of embodiment 2,4,5 and 6 gained.
the specific embodiment
Concrete steps of the present invention are:
(1) preparation of reduced graphene: take respectively 3 g graphite and 18 g potassium permanganate, after being ground, join formation suspension in the concentrated sulfuric acid (360ml) and phosphoric acid (40ml), suspension is incubated after 12 h at 50 ℃, be cooled to room temperature, be poured in 400 mL frozen water, after stirring, drip the H of 30 %
2o
2until be golden yellow, continue to be stirred to still after, centrifugal, taking precipitate, washs by 10 %HCl solution and deionized water respectively, until occur that colloid substance cannot be centrifugal.Take out colloid substance, by dialysis, make the ion concentration of sol solution be less than 5 ppm.Jelly is diluted to after desired concn by deionized water, utilizes ultrasonication that graphite oxide is peeled off, obtain graphene oxide.Get appropriate above-mentioned graphene oxide, add a certain amount of vitamin C (VC) solution, stir, it is incubated after 50 min at 95 ℃, obtain reduced graphene.
(2) preparation of Graphene/bismuth molybdate two-phase compound: the reduced graphene of 0.1 %-0.4 % load capacity is joined respectively in polytetrafluoroethylene (PTFE) reactor, stir, splash into respectively Bi (NO
3)
35H
2o (0.27M) and Na
2moO
42H
2the ethylene glycol solution of O (0.13M), after 10 min, drip NaOH (10 M) solution, regulate pH value to be about 9, continue to stir after 30 min, take off reactor and put into stainless steel outer lining, in the baking oven of 160-180 ℃, react 3-5 h, question response still is cooled to after room temperature, and the mixture in liner is carried out to centrifugation, the precipitation of gained successively, with distilled water and absolute ethanol washing, is ground standby in baking oven after 80 ℃ of oven dry.
(3) preparation of Graphene/bismuth molybdate/golden three-phase composite thing: take a certain amount of Graphene/bismuth molybdate compound of having prepared, put into beaker, add appropriate amount of deionized water, stir, splash into respectively different volumes chlorauric acid solution (10 mg/mL), stir 1-2 hour, under ultraviolet lamp, irradiate 2-4 h, centrifugal, dry, obtain Graphene/bismuth molybdate/golden three-phase composite compound.
Be below several embodiments of the present invention, further illustrate the present invention, but the present invention is not limited only to this.
embodiment 1: the preparation of reduced graphene
Take respectively 3 g graphite and 18 g potassium permanganate, after being ground, join formation suspension in the concentrated sulfuric acid (360 mL) and phosphoric acid (40 mL), suspension is incubated after 12 h at 50 ℃, be cooled to room temperature, be poured in 400 mL frozen water, after stirring, drip the H of 30 %
2o
2until be golden yellow, continue to be stirred to still after, centrifugal, taking precipitate, washs by 10 %HCl solution and deionized water respectively, until occur that colloid substance cannot be centrifugal.Take out colloid substance, by dialysis, make the ion concentration of sol solution be less than 5 ppm.Jelly is diluted to after desired concn by deionized water, utilizes ultrasonication that graphite oxide is peeled off, obtain graphene oxide.Get the above-mentioned graphene oxide of 100 mL, add 1 mL 0.1M vitamin C (VC) solution, stir, it is incubated after 50 min at 95 ℃, obtain reduced graphene.
embodiment 2: the preparation of Graphene/bismuth molybdate two-phase compound
Get reduced graphene 0.12 mL that embodiment 1 makes and join in polytetrafluoroethylene (PTFE) reactor, stir, splash into successively 15 mL Bi (NO
3)
35H
2o (0.27 M) and Na
2moO
42H
2the ethylene glycol solution of O (0.13 M), after 10 min, drip NaOH (10 M) solution, regulate pH value to be about 9, continue to stir after 30 min, take off reactor and put into stainless steel outer lining, in the baking oven of 160 ℃, react 3 h, question response still is cooled to after room temperature, mixture in liner is carried out to centrifugation, the precipitation of gained successively, with distilled water and absolute ethanol washing, is ground after 80 ℃ of oven dry in baking oven, and obtaining graphene-supported amount is Graphene/bismuth molybdate two-phase composite photo-catalyst of 0.1 %.
embodiment 3: the preparation of Graphene/bismuth molybdate two-phase compound
Get reduced graphene 0.24 mL that embodiment 1 makes and join in polytetrafluoroethylene (PTFE) reactor, stir, splash into successively 15 mL Bi (NO
3)
35H
2o (0.27 M) and Na
2moO
42H
2the ethylene glycol solution of O (0.13M), after 10 min, drip NaOH (10 M) solution, regulate pH value to be about 9, continue to stir after 30 min, take off reactor and put into stainless steel outer lining, in the baking oven of 160 ℃, react 3 h, question response still is cooled to after room temperature, mixture in liner is carried out to centrifugation, the precipitation of gained successively, with distilled water and absolute ethanol washing, is ground after 80 ℃ of oven dry in baking oven, and obtaining graphene-supported amount is Graphene/bismuth molybdate two-phase composite photo-catalyst of 0.2 %.
embodiment 4: the preparation of Graphene/bismuth molybdate/golden three-phase composite thing
Take Graphene/bismuth molybdate compound that 0.8 g embodiment 2 makes, put into beaker, add appropriate amount of deionized water, stir, splash into 80 μ L chlorauric acid solutions (10 mg/mL), stir one hour, in suspension, add ethanol again, under ultraviolet lamp, irradiate 4 h, centrifugal, dry, obtain Graphene/bismuth molybdate that golden load capacity is 0.1 %/golden three-phase composite compound.
embodiment 5: the preparation of Graphene/bismuth molybdate/golden three-phase composite thing
Take Graphene/bismuth molybdate compound that 0.8 g embodiment 2 makes, put into beaker, add appropriate amount of deionized water, stir, splash into 160 μ L chlorauric acid solutions (10 mg/mL), stir one hour, in suspension, add ethanol again, under ultraviolet lamp, irradiate 4 h, centrifugal, dry, obtain Graphene/bismuth molybdate that golden load capacity is 0.2 %/golden three-phase composite compound.
embodiment 6: the preparation of Graphene/bismuth molybdate/golden three-phase composite thing
Take Graphene/bismuth molybdate compound that 0.8 g embodiment 2 makes, put into beaker, add appropriate amount of deionized water, stir, splash into 320 μ L chlorauric acid solutions (10 mg/mL), stir one hour, in suspension, add ethanol again, under ultraviolet lamp, irradiate 4 h, centrifugal, dry, obtain Graphene/bismuth molybdate that golden load capacity is 0.4 %/golden three-phase composite compound.
Performance test
Fig. 1 is the powder X-ray RD figure of the Graphene/bismuth molybdate/golden three-phase composite photochemical catalyst of embodiment 2,4,5 and 6 gained.From figure, can find that prepared catalyst is the bismuth molybdate of orthorhombic crystal phase, the introducing of Graphene and gold grain does not change the crystalline phase of bismuth molybdate.
Fig. 2 is the powder TEM figure of the Graphene/bismuth molybdate/golden three-phase composite photochemical catalyst of embodiment 6 gained.Bismuth molybdate and Graphene structure in the form of sheets in the Graphene/bismuth molybdate/golden three-phase composite thing that can find to prepare from figure, the two close contact, gold grain is distributed on lamella.
Fig. 3 is the design sketch of the Graphene/bismuth molybdate/golden three-phase composite photocatalyst for degrading rhodamine B of embodiment 2,4,5 and 6 gained.Graphene/bismuth molybdate/golden three-phase composite photochemical catalyst visible light catalyst test, by rhodamine B degradation (1 × 10 under irradiating at 300 W xenon lamps
-5mol/L) characterize.Visible light catalytic reaction is carried out in HSX-F/UV 300 xenon source system and devices, and light source filters through optical filter, to guarantee that incident light is as visible ray (λ >420 nm); Catalyst amount is 40 mg.Before reaction, first adsorb 1 h make the rhodamine B illumination of turning on light after adsorption-desorption balance on catalyst turning on light.As can be seen from Figure 3 simultaneously load the activity of bismuth molybdate photocatalyst for degrading rhodamine B of gold and reduced graphene greatly improve.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. a three-phase composite visible light catalyst, is characterized in that: described catalyst is reduced graphene/Bi
2moO
6/ Au three-phase composite thing.
2. three-phase composite visible light catalyst according to claim 1, is characterized in that: in described three-phase composite thing, the mass percent of reduced graphene is 0.1%-0.4%, and the mass percent of Au is 0.1%-0.4%.
3. a method of preparing three-phase composite visible light catalyst as claimed in claim 1, is characterized in that: adopt chemical oxidization method to prepare Graphene, then Graphene reduction is formed to reduced graphene, adopt the synthetic reduced graphene/Bi of solvent-thermal method
2moO
6compound, then adopt dipping-reducing process that Au is carried on compound, form reduced graphene/Bi
2moO
6/ Au three-phase composite thing.
4. the preparation method of three-phase composite visible light catalyst according to claim 3, is characterized in that: comprise the following steps:
(1) preparation of reduced graphene
Take respectively 3 g graphite and 18 g potassium permanganate, after being ground, joining in the mixed liquor of the 360 mL concentrated sulfuric acids and 40 mL phosphoric acid and form suspension, at 50 ℃, be incubated after 12 h, be cooled to room temperature, be poured in 400 mL frozen water, after stirring, drip the H of 30wt.%
2o
2until be golden yellow, continue to be stirred to still after, centrifugal, HCl solution and the deionized water washing of 10wt.% for sediment, until occur that colloid substance cannot be centrifugal; Take out colloid substance, dialyse to ion concentration and be less than 5 ppm, with deionized water dilution, ultrasonic, obtain graphene oxide; Add vitamin c solution, stir, be incubated 50 min at 95 ℃, obtain reduced graphene;
(2) reduced graphene/Bi
2moO
6the preparation of compound
In reduced graphene, splash into while stirring 0.27 M Bi (NO
3)
35H
2o and 0.13 M Na
2moO
42H
2the ethylene glycol solution of O, after 10 min, drips 10 M NaOH solution, and regulating pH value is 9, continues to stir after 30 min, and 160 ℃ of reaction 3 h, are cooled to room temperature, centrifugation, and distilled water and absolute ethanol washing for sediment, 80 ℃ of oven dry obtain reduced graphene/Bi
2moO
6compound;
(3) reduced graphene/Bi
2moO
6the preparation of/Au three-phase composite thing
Take reduced graphene/Bi
2moO
6compound, adds deionized water, stirs, and splashes into 10 mg/mL chlorauric acid solutions, stirs 1 hour, irradiates 4 h under ultraviolet lamp, centrifugal, dries, and grinds and obtains reduced graphene/Bi
2moO
6/ Au three-phase composite thing.
5. an application for three-phase composite visible light catalyst as claimed in claim 1, is characterized in that: described catalyst is for liquid phase degradation of dye organic pollution.
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| CN113351221A (en) * | 2021-06-08 | 2021-09-07 | 常州大学 | Preparation method and application of graphene-based bismuth-series heterostructure catalyst |
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| CN113351221B (en) * | 2021-06-08 | 2023-09-29 | 常州大学 | Preparation method and application of graphene-based bismuth-based heterostructure catalyst |
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