CN102872851A - Preparation method of zinc oxide/attapulgite composite photocatalytic material - Google Patents
Preparation method of zinc oxide/attapulgite composite photocatalytic material Download PDFInfo
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- CN102872851A CN102872851A CN2012103830221A CN201210383022A CN102872851A CN 102872851 A CN102872851 A CN 102872851A CN 2012103830221 A CN2012103830221 A CN 2012103830221A CN 201210383022 A CN201210383022 A CN 201210383022A CN 102872851 A CN102872851 A CN 102872851A
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Abstract
The invention discloses a preparation method of a zinc oxide/attapulgite composite photocatalytic material. The method comprises the steps of dispersing the attapulgite in an alcoholic solution under the assistance of ultrasonic, adding Zn(OAC)2.6H2O, heating to make Zn(OAC)2.6H2O dissolved completely while stirring, cooling to a room temperature; reacting for a certain time under the assistance of ultrasonic; precipitating, filtering, washing and drying. The method is simple in operation, has fast reaction rate and high yield, is in no need of high-temperature calcination, is green and safe, and is energy conservation and environment protection.
Description
Technical field
The invention belongs to field of environment protection, be specifically related to the preparation method of a kind of zinc oxide/attapulgite composite photocatalyst material.
Background technology
The Nano semiconductor photocatalysis technology is subject to extensive concern as a kind of effective environmental contaminants improvement method.Nano zine oxide is the several oxide semiconductor materials that can realize quantum size effect of only a few, under certain conditions, has the TiO of ratio
2Higher photocatalysis performance is demonstrating good application prospect aspect the photocatalytic degradation organic wastewater.Yet, in actual use, because the photocatalyst granular that is suspended in the solution is tiny, there is defectives such as easily outflowing with water, reclaim difficulty, photochemical catalyst is fixed on the suitable carrier and can effectively addresses this problem.
Attapulgite is a kind of crystalloid hydrous magnesium aluminium silicate mineral with unique chain layer structure, has specific area large, and chemical stability is good, and the characteristics such as high adsorption capacity have a wide range of applications in fields such as building materials, environmental protection, chemical industry, food, medicine, agriculturals.Catalysis material is fixed on the attapulgite, not only can solve photochemical catalyst recovery hard problem in the actual use procedure, and absorption property and the catalysis material of attapulgite excellence can be organically combined, increase the specific area of light-catalyzed reaction, improve light-catalyzed reaction speed and efficient.
Patent (publication number: CN101444717A) disclose a kind of preparation method of concavo-convex rod soil/zinc oxide nanometer, the method is take zinc salt and carbonate as raw material, at first zinc salt and carbonate solution are joined in the attapulgite dispersion liquid, filter after stirring 0.5-5h, get at 300-600 ℃ of lower high-temperature calcination 1-10h after the filter cake that obtains is fully washed.The method not only preparation time is long, and needs high-temperature calcination, consumes a large amount of energy.
Summary of the invention
The objective of the invention is for overcoming above-mentioned the deficiencies in the prior art, a kind of environment-friendly preparation method thereof of convenient to operation, cost is low, energy resource consumption is few zinc oxide/attapulgite composite photocatalyst material is provided.
The technical solution adopted in the present invention is: at first be dispersed in the alcoholic solution attapulgite is ultrasonic, then add Zn (OAC)
26H
2O stirs lower heating and makes Zn (OAC)
26H
2After O dissolves fully, cool to room temperature, ultrasonic reaction certain hour then, sedimentation and filtration, washing, oven dry and get.
The preparation method of zinc oxide provided by the invention/attapulgite composite photocatalyst material carries out according to following steps: (1) is scattered in the attapulgite powder in the alcoholic solution with solid-liquid mass volume ratio (g:ml) 1:10-1:30, ultrasonic processing 10-30min makes attapulgite suspension; With Zn (OAC)
26H
2O joins in the attapulgite suspension, is heated to 100-120 ℃ under stirring, and treats Zn (OAC)
26H
2O is down to room temperature after dissolving fully, obtains containing the attapulgite suspension of zinc acetate presoma; The attapulgite suspension that (2) will contain the zinc acetate presoma changes in the ultrasonic reactor, titanium alloy ultrasonic probe (tip diameter 15mm) is immersed in the reactant liquor, ultrasonic reaction, after question response finishes, be cooled to room temperature, behind the sedimentation and filtration, with absolute ethyl alcohol, distilled water washing, oven dry, namely get zinc oxide/attapulgite composite photocatalyst material respectively.
As shown from the above technical solution: the present invention at first adopts the mode of ultrasonic dispersion to prepare the pure suspension of attapulgite, and hyperacoustic cavitation produces huge impulsive force and microjet, and under its effect, fibrous attapulgite aggregation is well disperseed; Zinc acetate is a kind of lewis acid, and the cloud density on the carbonylic carbon atom is lower, and the oxygen atom nucleophilic attack carboxyl carbon atom on the alcoholic extract hydroxyl group under the ultrasonic cavitation effect produces moment HTHP, forms Zn (OH)
2And further the concrete reaction mechanism mechanism of reaction of dehydration production ZnO(is seen accompanying drawing 3).Alcohol is reaction medium, participates in reaction as nucleopilic reagent again, and while or the growth control agent of zinc oxide stop the reunion of zinc oxide/attapulgite particle in the preparation process.
As preferably, the alcohol described in the step (1) is: a kind of in 1,2-PD, 1,3-PD, diglycol, the BDO; These pure boiling points are high, under hyperacoustic effect, easily produce the HTHP of moment in solution, are beneficial to the generation of ZnO.
As preferentially, the consumption of the zinc acetate described in the step (1) accounts for the 10-90% of attapulgite quality to generate the quality of ZnO; The consumption of zinc acetate is excessively low, and meeting is so that the catalytic effect of the zinc oxide of preparation/attapulgite composite photo-catalyst is poor; The consumption of zinc acetate is too high, affects the recovery of zinc oxide/attapulgite composite photo-catalyst.
As preferably, the ultrasonic reaction power described in the step (2) is 360W-1800W, ultrasonic time 30-120min.Ultrasonic power is excessively low, ultrasonic time is too short, is unfavorable for the generation of ZnO; Ultrasonic power is too high, ultrasonic time is long, not only wastes resource, and can cause solution overheated, the reunion of aggravation particle.
Compared with prior art, the present invention has the following advantages:
(1) the present invention utilizes the ultrasonic cavitation effect that fibrous attapulgite aggregation is well disperseed in alcoholic solution; The HTHP making ZnO that utilizes cavitation to produce, simple to operate, reaction rate is fast, and productive rate is high, and particle size, pattern are easy to control;
(2) the present invention selects zinc acetate and alcohol as reactant, need not to add other poisonous and harmful chemicals, and reaction need not high-temperature calcination, green safety, energy-conserving and environment-protective after finishing;
(3) alcohol is solvent, participates in reaction as nucleopilic reagent again, and while or the growth control agent of zinc oxide stop the reunion of zinc oxide/attapulgite particle in the preparation process.
Description of drawings
Fig. 1 is the XRD figure of attapulgite (ATP), embodiment 2 gained zinc oxide/attapulgite (ZnO/ATP) composite photocatalyst materials.
Fig. 2 is the XRD figure of embodiment 6, embodiment 7 resulting materials
Fig. 3 is that zinc acetate reacts the ZnO reaction mechanism mechanism of reaction (take diethylene glycol as example) that generates with alcohol
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.Should be understood that these embodiment just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Photocatalysis performance is estimated: the material that takes by weighing respectively preparation among the 50mg embodiment 1～7 joins in the methylene blue solution that 80mL concentration is 50mg/L, place the dark place to stir 2h solution, after the balance upon adsorption, UV light (power 15W, wavelength 365nm) irradiation, light source distance liquid level distance is 10cm, after illumination finishes, get 5mL reaction suspension, get supernatant liquor after (10000r/min) centrifugation at a high speed, under λ max, measure the absorbance of solution with the 722s visible spectrophotometer.Be calculated as follows degradation rate.
In the formula: η is degradation rate, C
0Before light degradation, the concentration of methylene blue solution, C
tFor illumination t constantly after, the concentration of methylene blue solution.
Embodiment 1
(1) 10g attapulgite powder is scattered in the 100mL 1,2-PD solution, ultrasonic processing 30min makes attapulgite suspension; With 2.71g Zn (OAC)
26H
2O joins in the attapulgite suspension, is heated to 100 ℃ under stirring, and treats Zn (OAC)
26H
2O is down to room temperature after dissolving fully, obtains containing the attapulgite suspension of zinc acetate presoma;
The attapulgite suspension that (2) will contain the zinc acetate presoma changes in the ultrasonic reactor, titanium alloy ultrasonic probe (tip diameter 15mm) is immersed in the reactant liquor, ultrasonic reaction, ultrasonic power 360W, ultrasonic time 120min, after question response finishes, be cooled to room temperature, behind the sedimentation and filtration, respectively with after absolute ethyl alcohol, the distilled water washing, oven dry namely gets zinc oxide/attapulgite composite photocatalyst material.
After the light-catalyzed reaction 2 hours, this composite is 88.5%. to the degradation rate of methylene blue
Embodiment 2
(1) 10g attapulgite powder is scattered in the 300mL BDO solution, ultrasonic processing 10min makes attapulgite suspension; With 24.39g Zn (OAC)
26H
2O joins in the attapulgite suspension, is heated to 120 ℃ under stirring, and treats Zn (OAC)
26H
2O is down to room temperature after dissolving fully, obtains containing the attapulgite suspension of zinc acetate presoma;
The attapulgite suspension that (2) will contain the zinc acetate presoma changes in the ultrasonic reactor, titanium alloy ultrasonic probe (tip diameter 15mm) is immersed in the reactant liquor, ultrasonic reaction, ultrasonic power 1800W, ultrasonic time 30min, after question response finishes, be cooled to room temperature, behind the sedimentation and filtration, respectively with after absolute ethyl alcohol, the distilled water washing, oven dry namely gets zinc oxide/attapulgite composite photocatalyst material.
After the light-catalyzed reaction 2 hours, this composite is 92.1%. to the degradation rate of methylene blue
Embodiment 3
(1) 10g attapulgite powder is scattered in the 200mL diglycol solution, ultrasonic processing 20min makes attapulgite suspension; With 13.55g Zn (OAC)
26H
2O joins in the attapulgite suspension, is heated to 110 ℃ under stirring, and treats Zn (OAC)
26H
2O is down to room temperature after dissolving fully, obtains containing the attapulgite suspension of zinc acetate presoma;
The attapulgite suspension that (2) will contain the zinc acetate presoma changes in the ultrasonic reactor, titanium alloy ultrasonic probe (tip diameter 15mm) is immersed in the reactant liquor, ultrasonic reaction, ultrasonic power 1260W, ultrasonic time 30min, after question response finishes, be cooled to room temperature, behind the sedimentation and filtration, respectively with after absolute ethyl alcohol, the distilled water washing, oven dry namely gets zinc oxide/attapulgite composite photocatalyst material.
After the light-catalyzed reaction 2 hours, this composite is 93.6%. to the degradation rate of methylene blue
Embodiment 4
(1) 10g attapulgite powder is scattered in the 200mL 1,3-PD solution, ultrasonic processing 10min makes attapulgite suspension; With 8.13g Zn (OAC)
26H
2O joins in the attapulgite suspension, is heated to 100 ℃ under stirring, and treats Zn (OAC)
26H
2O is down to room temperature after dissolving fully, obtains containing the attapulgite suspension of zinc acetate presoma;
The attapulgite suspension that (2) will contain the zinc acetate presoma changes in the ultrasonic reactor, titanium alloy ultrasonic probe (tip diameter 15mm) is immersed in the reactant liquor, ultrasonic reaction, ultrasonic power 720W, ultrasonic time 60min, after question response finishes, be cooled to room temperature, behind the sedimentation and filtration, respectively with after absolute ethyl alcohol, the distilled water washing, oven dry namely gets zinc oxide/attapulgite composite photocatalyst material.
After the light-catalyzed reaction 2 hours, this composite is 91.4%. to the degradation rate of methylene blue
Embodiment 5
(1) 10g attapulgite powder is scattered in the 100mL diglycol solution, ultrasonic processing 30min makes attapulgite suspension; With 18.97g Zn (OAC)
26H
2O joins in the attapulgite suspension, is heated to 110 ℃ under stirring, and treats Zn (OAC)
26H
2O is down to room temperature after dissolving fully, obtains containing the attapulgite suspension of zinc acetate presoma;
The attapulgite suspension that (2) will contain the zinc acetate presoma changes in the ultrasonic reactor, titanium alloy ultrasonic probe (tip diameter 15mm) is immersed in the reactant liquor, ultrasonic reaction, ultrasonic power 1080W, ultrasonic time 60min, after question response finishes, be cooled to room temperature, behind the sedimentation and filtration, respectively with after absolute ethyl alcohol, the distilled water washing, oven dry namely gets zinc oxide/attapulgite composite photocatalyst material.
After the light-catalyzed reaction 2 hours, this composite is 95.2%. to the degradation rate of methylene blue
Embodiment 6
(1) 10g attapulgite powder is scattered in the 100mL diglycol solution, ultrasonic processing 30min makes attapulgite suspension; With 18.97g Zn (NO
3)
26H
2O joins in the attapulgite suspension, is heated to 110 ℃ under stirring, and treats Zn (NO
3)
26H
2O is down to room temperature after dissolving fully, obtains containing the attapulgite suspension of zinc nitrate presoma;
The attapulgite suspension that (2) will contain the zinc nitrate presoma changes in the ultrasonic reactor, titanium alloy ultrasonic probe (tip diameter 15mm) is immersed in the reactant liquor, ultrasonic reaction, ultrasonic power 1080W, ultrasonic time 60min is after question response finishes, be cooled to room temperature, behind the sedimentation and filtration, respectively with after absolute ethyl alcohol, the distilled water washing, oven dry.Product X RD test result is seen accompanying drawing 2.Photocatalysis is tested and is shown, under the UV-irradiation, this product can't the photocatalytic degradation methylene blue.
Embodiment 7
(1) 10g attapulgite powder is scattered in the 100mL aqueous isopropanol, ultrasonic processing 30min makes attapulgite suspension; With 18.97g Zn (OAC)
26H
2O joins in the attapulgite suspension, is heated to 110 ℃ under stirring, and treats Zn (OAC)
26H
2O is down to room temperature after dissolving fully, obtains containing the attapulgite suspension of zinc acetate presoma;
The attapulgite suspension that (2) will contain the zinc acetate presoma changes in the ultrasonic reactor, titanium alloy ultrasonic probe (tip diameter 15mm) is immersed in the reactant liquor, ultrasonic reaction, ultrasonic power 1080W, ultrasonic time 60min is after question response finishes, be cooled to room temperature, behind the sedimentation and filtration, respectively with after absolute ethyl alcohol, the distilled water washing, oven dry.Product X RD test result is seen accompanying drawing 2.Photocatalysis is tested and is shown, under the UV-irradiation, this product can't the photocatalytic degradation methylene blue.
Claims (5)
1. the preparation method of zinc oxide/attapulgite composite photocatalyst material is characterized in that this preparation method adopts following steps: be dispersed in the alcoholic solution attapulgite is ultrasonic, then add Zn (OAC)
26H
2O stirs lower heating and makes Zn (OAC)
26H
2After O dissolves fully, cool to room temperature, ultrasonic reaction certain hour then, sedimentation and filtration, washing, oven dry and get.
2. the preparation method of zinc oxide claimed in claim 1/attapulgite composite photocatalyst material is characterized in that this preparation method adopts following steps:
(1) the attapulgite powder is scattered in the alcoholic solution with solid-liquid mass volume ratio 1:10-1:30, ultrasonic processing 10-30min makes attapulgite suspension; With Zn (OAC)
26H
2O joins in the attapulgite suspension, is heated to 100-120 ℃ under stirring, and treats Zn (OAC)
26H
2O is down to room temperature after dissolving fully, obtains containing the attapulgite suspension of zinc acetate presoma;
The attapulgite suspension that (2) will contain the zinc acetate presoma changes in the ultrasonic reactor, the titanium alloy ultrasonic probe is immersed in the reactant liquor, ultrasonic reaction, after question response finishes, be cooled to room temperature, behind the sedimentation and filtration, respectively with after absolute ethyl alcohol, the distilled water washing, oven dry namely gets zinc oxide/attapulgite composite photocatalyst material.
3. the preparation method of a kind of zinc oxide according to claim 1/attapulgite composite photocatalyst material, it is characterized in that: described alcohol is: a kind of in 1,2-PD, 1,3-PD, diglycol, the BDO.
4. the preparation method of a kind of zinc oxide according to claim 2/attapulgite composite photocatalyst material is characterized in that: the consumption of zinc acetate accounts for the 10-90% of attapulgite quality to generate the quality of ZnO.
5. the preparation method of a kind of zinc oxide according to claim 2/attapulgite composite photocatalyst material, it is characterized in that: the ultrasonic reaction power described in the step (2) is 360W-1800W, ultrasonic time 30-120min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108479777A (en) * | 2018-03-28 | 2018-09-04 | 常州大学 | A kind of preparation method and applications of attapulgite composite photo-catalyst |
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