CN104276606A - Preparation method, application and regenerating method of silicon magnetic hollow sphere ZnSixFe2-xO4 - Google Patents
Preparation method, application and regenerating method of silicon magnetic hollow sphere ZnSixFe2-xO4 Download PDFInfo
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- CN104276606A CN104276606A CN201410369231.XA CN201410369231A CN104276606A CN 104276606 A CN104276606 A CN 104276606A CN 201410369231 A CN201410369231 A CN 201410369231A CN 104276606 A CN104276606 A CN 104276606A
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Abstract
The invention discloses a preparation method, application and a regenerating method of a silicon magnetic hollow sphere ZnSixFe2-xO4, and relates to the technical field of adsorption materials, photocatalytic materials and wastewater treatment. The preparation method of the silicon magnetic hollow sphere ZnSixFe2-xO4 comprises the following steps: weighing and dissolving silicate, a ferric salt and a zinc salt in an alcohol-aqueous liquid; stirring and regulating the pH value of the liquid to 6.5-7.5, stirring at 50-70 DEG C, cooling and ageing; layering and removing the supernatant liquid, washing solid-phase matters with distilled water by many times until the solid-phase matters are neutral, and then washing the solid-phase matters with absolute ethyl alcohol; drying the solids in vacuum until the weight is constant, and calcining the solids to obtain the silicon magnetic hollow sphere. The silicon magnetic hollow sphere prepared by the preparation method can be used as a wastewater treating agent and also can be used as an antibacterial agent. When used as the wastewater treating agent, the silicon magnetic hollow sphere has good adsorption effects and photocatalysis. The preparation process is relatively simple, energy-saving and environmentally friendly; products can be conveniently separated and recycled, and can be recycled after being activated and regenerated, and thus, the preparation method has the advantages of being time-saving, safe, efficient, low in price and continuous in separating and recycling.
Description
Technical field
The present invention relates to sorbing material, photocatalyst material and technical field of waste water processing, specifically refer to a kind of waste water conditioner capable of magnetic separating-silicon magnetic hollow ball ZnSi
xfe
2-xo
4the method of the preparation method of mixture, application and regeneration.
Background technology
21 century, environment, the energy and health are the hot issues that people are concerned about most.Efficient adsorption technology, Photocatalitic Technique of Semiconductor be we provide a kind ofly effectively to curb environmental pollution, efficiency utilization sun power and suppress the effective way of unwanted bacteria.But single material is difficult to meet multi-functional requirement.In order to overcome this shortcoming, investigator utilizes doping to build matrix material to expand the performance of single-material, makes it the demand of As soon as possible Promising Policy multifunction.
Ferrite is important and the most ripe magneticsubstance as a class, because it has the concern that regulatable saturation magnetization, coercive force and magnetocrystalline anisotropy are subject to investigator always, and be widely used in various field, such as magneticsubstance and device, magnetic recording storage medium, medical target material and electromagnetic shielding etc.Because the ferritic physical and chemical performance of micro/nano level affects highly significant by its particle diameter and pattern, therefore, different and ferrite that is morphology controllable becomes one of focus of research at present, wherein the new function material of the hollow ball ferrite of micro/nano level and conductor oxidate doping thereof possesses some peculiar properties especially, specific surface area is large, density is low, photocatalysis performance and good adsorption performance, at absorption and photocatalysis degradation organic contaminant, the fields such as suppression and kill harmful bacterium obtain and apply widely, field of medicaments can also be used for as drug targeting carrier.
The preparation method of hollow ball micro-nanometer structural material generally has two kinds of approach, and one is template, and template used comprises hard template and soft template, as polymer microballoon, silicon-dioxide, drop, and microemulsion, polymer micelle etc.; Two is utilize some physical principles, as Kirkendall effect, Ostwald ageing and LBL layer-by-layer etc.
Chinese invention patent " a kind of method preparing hollow magnetic ball " (CN1761003A) be with the carboxylic polymer emulsion of rich surface for template, be rich in the metal hydroxides of hydroxyl at its Surface coating, through Overheating Treatment obtain hollow magnetic ball; Chinese invention patent " a kind of spinel type ferrite magnetic hollow microsphere and preparation method thereof " (CN101274847A) report is core with sulfonated polystyrene, first grow di-hydroxyl composite metal oxidate by coprecipitation method at its surface in situ, finally calcining obtains spinel magnetic hollow microsphere; Chinese invention patent " a kind of method of producing size-controllable magnetic hollow spheres " (CN101444712A) is template with monodisperse polystyrene ball, there is coprecipitation reaction and generate ferrite precursor in inorganic metal salt, then obtain hollow magnetic ball through Overheating Treatment under the effect of precipitation agent sodium hydroxide; In addition, Chinese invention patent " one step synthesis of amphoteric super-paramagnetic submicro inorganic thing/polymer composite hollow ball " (CN1844201A), " a kind of synthetic method of ferrimagnetism hollow microballoons " (CN101333103A) and " a kind of preparation method of nano hollow microballoons of spinelle type ferrite " all adopt solvent-thermal method to prepare ferrite hollow microspheres by metal salt solution and tensio-active agent.
As can be seen from above patent, the preparation method of micro/nano level ferrite hollow ball almost adopts template, general steps is all that first to synthesize pattern be spherical template, then makes reaction product or precursor deposition or accumulates in the surface of template, last thermal treatment removing template.Its preparation process is not only loaded down with trivial details, and its template as " sacrificial core " from being generated to removing, will certainly production efficiency be affected, consume more raw material, therefore its actual application value is not remarkable.
Summary of the invention
The present invention is intended to provide a kind of with low cost, easy to operate, silicon magnetic hollow ball ZnSi of carrying out Separation and Recovery with magnetic separation technique
xfe
2-xo
4preparation method and application.
Silicon magnetic hollow ball ZnSi
xfe
2-xo
4preparation method, it is characterized in that, comprise the steps:
A. take positive silicon ester, molysite and zinc salt, the amount of substance of three is than being x:2-x:1 (x=0.2,0.4,0.6,0.8,1.0), and be dissolved in ethanol-water solution, the span of ethanol, water volume ratio is 1:1 ~ 5:1; Be stirred to solution transparent;
B. use urea regulator solution pH value to 6.5 ~ 7.5,50 ~ 70 DEG C are stirred 1.5 ~ 2.5 h, are cooled to room temperature, ageing 3.5 ~ 4.5 h;
C. the reaction system layering in step b is removed supernatant liquid, distilled water repeatedly washs solid formation to neutral, then uses washes of absolute alcohol;
D. by solids vacuum-drying to constant weight, calcining, obtain silicon magnetic hollow ball ZnSi
xfe
2-xo
4.
Use silicon magnetic hollow ball ZnSi prepared by the disclosed method of invention
xfe
2-xo
4there is process organic pollutant and degerming function; Organic pollutant comprises tropeolin-D, methylene blue, rhodamine B, phenols, kerosene, diesel oil, machine oil; The bacterium that can suppress and kill comprises intestinal bacteria, streptococcus aureus and Candida albicans.
The product of invention preparation both as waste water conditioner, also can be used as antiseptic-germicide.As waste water conditioner, there is good adsorption and photocatalysis; The inventive method adopts directly prepares ferrite hollow ball without mould plate technique single stage method, and more environmental protection simpler, more energy-conservation than the technique of traditional mould plate technique and sintering technology; The product prepared by the present invention has magnetic functional performance, and available magnetic separation technique is separated easily, reclaims product, and activated regeneration can be recycled, have save time, safe, efficient, inexpensive and the advantage of recovery can be continuously separated.
accompanying drawing illustrates:
Accompanying drawing of the present invention is described as follows:
Fig. 1 silicon magnetic hollow ball ZnSi
xfe
2-xo
4xRD figure spectrum (a.x=0.2, b.x=0.4, c.x=0.6, d.x=0.8);
Fig. 2 silicon magnetic hollow ball ZnSi
0.4fe
1.6o
4sEM (a, b) and TEM (c);
Fig. 3 silicon magnetic hollow ball ZnSi
0.4fe
1.6o
4middle Zn (a), Ti (b), Fe (c) scheme with the Mapping of O (d) element.
embodiment:
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described as follows, special declaration: following embodiment is described further method of the present invention.Protection scope of the present invention not by the restriction of embodiment, and is determined by claims.Experimental technique in following embodiment, is ordinary method if no special instructions; Material used in example, if no special instructions, all purchased from conventional chemical Reagent Company.
Silicon magnetic hollow ball ZnSi
xfe
2-xo
4preparation method, it is characterized in that, comprise the steps:
A. take positive silicon ester, molysite and zinc salt, the amount of substance of three is than being x:2-x:1 (x=0.2,0.4,0.6,0.8,1.0), and be dissolved in ethanol-water solution, the span of ethanol, water volume ratio is 1:1 ~ 5:1; Be stirred to solution transparent;
B. use urea regulator solution pH value to 6.5 ~ 7.5,50 ~ 70 DEG C are stirred 1.5 ~ 2.5 h, are cooled to room temperature, ageing 3.5 ~ 4.5 h;
C. the reaction system layering in step b is removed supernatant liquid, distilled water repeatedly washs solid formation to neutral, then uses washes of absolute alcohol;
D. by solids vacuum-drying to constant weight, calcining, obtain silicon magnetic hollow ball ZnSi
xfe
2-xo
4.
As the important improvement of the present invention relative to prior art, urea regulator solution pH value in described step b, is selected to be 6.5 ~ 7.5.Use urea can reduce production cost greatly as reagent, hydrolysis of urea produces two kinds of materials, and one is weakly alkaline NH
3, make metal ion generation hydrolysis reaction generate oxyhydroxide; Another kind is that carbonic acid gas bubble is equivalent to gas phase template, and the reaction of generation oxyhydroxide is carried out around bubble, thus forms cavity; Oxyhydroxide is made to decompose the ferrite generating magnetic finally by sintering.From the hollow formation mechenism of analysis, control the pH value of solution, the self-assembly of ferrite hollow ball is formed and plays conclusive effect.And have selected cheap urea on the basis ensureing quality product, greatly reduce production cost.Therefore, not only method is simple in the present invention, raw material is inexpensive, and the ferrite hollow ball the obtained single thing phase that to be crystallization good, without other impurity, hollow ball size is 250 ~ 500 nm, and wall thickness is 50 ~ 100 nm, specific surface area about 68.56 cm3/g, saturation magnetization is 35 ~ 50 emu/g, and coercive force is 100 ~ 300 Oe.
When needing to carry out layering to reaction system in step c, after the throw out in magnetite absorption reaction system can be used to make itself and solution layering, then remove supernatant liquid.Utilize the magnetic interaction between magnetite and throw out (magnetic), reach fast hierarchical, and can effectively reduce sedimentary loss.
Use silicon magnetic hollow ball ZnSi prepared by the disclosed method of invention
xfe
2-xo
4there is process organic pollutant and degerming function; Organic pollutant comprises tropeolin-D, methylene blue, rhodamine B, phenols, kerosene, diesel oil, machine oil; The bacterium that can suppress and kill comprises intestinal bacteria, streptococcus aureus and Candida albicans.
After utilizing technical scheme disclosed in the present invention to use as organic sewage treatment agent or antiseptic-germicide, can treatedly recycle, the renovation process recycled is: by the silicon magnetic hollow ball ZnSi after use
xfe
2-xo
4be placed in organic solvent or acid-base solution, supersound process 0.5 ~ 1 h, stir 1 ~ 2 h, filter after Magneto separate; Solid matter, through 400 ~ 600 DEG C of process 1 ~ 2 h, obtains the product of regeneration, for recycling.
In the present invention, preparing product to the testing method of water treatment effect is: in several Erlenmeyer flasks, pour experiment waste water 50 mL into, the pH value of waste water is regulated with hydrochloric acid or sodium hydroxide solution, add the product obtained in the present invention, low rate mixing after ultrasonic disperse, after Magneto separate sedimentation, supernatant liquid is isolated with decantation, by its absorbancy of spectrophotometric determination, according to the concentration of typical curve determination pollutent, thus calculate the loading capacity of product and the clearance to pollutent.
In the present invention, the antibacterial and antibacterial effect of products obtained therefrom adopts antibacterial circle diameter and minimal inhibitory concentration to represent respectively, and tests with pressed powder inhibition zone method and test tube doubling dilution respectively.Testing method Liang Xiaoxi, Chen Keyu, Li Liang are superfine at " Cu
0.05zn
0.95the preparation of O/ polypyrrole nano-complex and anti-microbial property ", Chinese science. chemistry, method disclosed in 2013,43:840 ~ 847.
For further illustrating preparation method disclosed in the present invention, material is selected as follows:
Positive silicon ester is any one in tetraethoxy, positive silicic acid propyl ester and butyl silicate, and its consumption is 0.2 ~ 3 mmol; Molysite and zinc salt are any one in nitrate, vitriol or muriate etc., and the consumption of molysite is 1 ~ 5.4 mmol, the consumption of zinc salt is 1 ~ 3 mmol; Volume 30 ~ 150 mL of ethanol-distilled water solution, its volume ratio n=1:1 ~ 5:1; The consumption of urea is 1.5 ~ 3.0 g; Calcining temperature is 400 ~ 600 ° of C, and sintering time is 2 ~ 4 h.
embodiment 1:ZnSi
0.2
fe
1.8
o
4
silicon magnetic hollow ball
1. the preparation of product
A. 0.0413 ~ 0.1239 g tetraethyl orthosilicate, 0.7271 ~ 2.1813 g Fe (NO3) is accurately taken
39H
2o and 0.2974 ~ 0.8922 g Zn (NO3)
26H2O, join in 30 ~ 150 mL ethanol-water solutions, ethanol, water volume ratio are 2:1, are stirred to solution transparent;
B. adding 1.5 ~ 2.1 g urea regulator solution pH value to this solution is 6.5 ~ 7.5,50 ~ 70 DEG C of stirring 2 h, is cooled to room temperature, ageing 4 h.
C. utilize magnetite make its layering and remove supernatant liquid, repeatedly wash solid formation to neutral with distilled water, then use washes of absolute alcohol;
D. by solid formation vacuum-drying to constant weight, 400 ~ 600 DEG C calcining 1 ~ 2 h, obtain silicon magnetic hollow ball ZnSi
0.2fe
1.8o
4.
2. apply
(1) by 25 mg ZnSi
0.2fe
1.8o
4it is in the methyl orange solution of 50 mg/L that hollow ball joins 50 mL concentration, and control pH is 6.0 ~ 7.0, and ultrasonic disperse 0.5 ~ 1 h, stirs 30 min under natural light, after Magneto separate sedimentation, gets supernatant liquid and measures its ultraviolet-visible absorption spectroscopy.Result shows, the absorption-degradation efficiency of product to tropeolin-D reaches 93.8; Effect after recycling for 5 times is not less than 91.4 %.
(2) by 25 mg ZnSi
0.2fe
1.8o
4it is in the methylene blue solution of 50 mg/L that hollow ball joins 50 mL concentration, and control pH is about 5 ~ 6, by the method process of (1).Result shows, the absorption-degradation efficiency of product to methylene blue reaches 92.6 %; Effect after recycling for 5 times is not less than 91 %.
(3) by 25 mg ZnSi
0.2fe
1.8o
4it is that in the rhodamine B solution of 50 mg/L, control pH is about 5 ~ 6 that hollow ball joins 50 mL concentration, by the method process of (1).Result shows, the absorption-degradation efficiency of product to rhodamine B reaches 94.8 %; Effect after recycling for 5 times is not less than 92.5 %.
(4) by 25 mg ZnSi
0.2fe
1.8o
4it is that in the Acid Red B solution of 50 mg/L, control pH is about 5.5 ~ 6.0 that hollow ball joins 50 mL concentration, by the method process of (1).Result shows, the absorption-degradation efficiency of product to Acid Red B reaches 92. 3 %; Effect after recycling for 5 times is not less than 89 %.
(5) by 25 mg ZnSi
0.2fe
1.8o
4it is that in the diesel fuel-water solution of 20 mg/L, control pH is about 6.0 ~ 7.0 that hollow ball joins 50 mL concentration, by the method process of (1).Result shows, the absorption-degradation efficiency of product to diesel oil reaches 91.7 %; Effect after recycling for 5 times is not less than 87.5 %.
embodiment 2:ZnSi
0.4
fe
1.6
o
4
silicon magnetic hollow ball
1. the preparation of product
A. 0.0825 ~ 0.2475 g tetraethyl orthosilicate, 0.6463 ~ 1.9389 g Fe (NO3) is accurately taken
39H
2o and 0.2974 ~ 0.8922 g Zn (NO3)
26H
2o, join in 30 ~ 150 mL ethanol-water solutions, ethanol, water volume ratio are 3:1, are stirred to solution transparent;
B. adding 1.5 ~ 2.1 g urea regulator solution pH value to this solution is 6.5 ~ 7.5,50 ~ 70 DEG C of stirring 2 h, cools throw out to room temperature, ageing 4 h.
C. utilize magnetite make its layering and remove supernatant liquid, repeatedly wash solid formation to neutral with distilled water, then use washes of absolute alcohol;
D. by solid formation vacuum-drying to constant weight, 400 ~ 600 DEG C calcining 1 ~ 2 h, obtain silicon magnetic hollow ball ZnSi
0.4fe
1.6o
4.
2. apply
(1) by 25 mgZnSi
0.4fe
1.6o
4it is in the methyl orange solution of 50 mg/L that hollow ball joins 50 mL concentration, and control pH is about 5.5, ultrasonic disperse 0.5 h, low rate mixing 30 min under natural light, after Magneto separate sedimentation, gets supernatant liquid and measures its ultraviolet-visible absorption spectroscopy.Result shows, the absorption-degradation efficiency of product to tropeolin-D reaches 94.4 %; Effect after recycling for 5 times is not less than 91.6 %.
(2) by 25 mg ZnSi
0.4fe
1.6o
4it is in the rhodamine B solution of 50 mg/L that hollow ball joins 50 mL concentration, and control pH is 5 ~ 6, by the method process of (1).Result shows, the absorption-degradation efficiency of product to rhodamine B reaches 93.6 %; Effect after recycling for 5 times is not less than 91 %.
(3) by 25 mg ZnSi
0.4fe
1.6o
4hollow ball join 50 mL concentration be 50 mg/L Acid Red B solution in, control pH is 5.5 ~ 6.0, by the method process of (1).Result shows, the absorption-degradation efficiency of product to Acid Red B reaches 92.4 %; Effect after recycling for 5 times is not less than 89.5 %.
(4) by 25 mg ZnSi
0.4fe
1.6o
4it is in the methylene blue solution of 50 mg/L that hollow ball joins 50 mL concentration, and control pH is about 6, by the method process of (1).Result shows, the absorption-degradation efficiency of product to methylene blue reaches 92.8 %; Effect after recycling for 5 times is not less than 91 %.
(5) by 25 mg ZnSi
0.4fe
1.6o
4it is in the diesel fuel-water solution of 20 mg/L that hollow ball joins 50 mL concentration, and control pH is 6.0 ~ 6.5, by the method process of (1).Result shows, the absorption-degradation efficiency of product to diesel oil reaches 92.8 %; Effect after recycling for 5 times is not less than 90.5 %.
(6) with intestinal bacteria (E. Coli), streptococcus aureus (S. Aureus) and Candida albicans (C. Albicans) for test bacterial classification, adopt the antibacterial circle diameter of pressed powder inhibition zone method and test tube doubling dilution test products and minimal inhibitory concentration respectively. result shows, product is to E. Coli), the antibacterial circle diameter of S. Aureus and C. Albicans and minimal inhibitory concentration be respectively 32.8,31.4,35.1 mm and 25,25,12.5 μ g/mL.
embodiment 3: silicon magnetic hollow ball ZnSi
0.6
fe
1.4
o
4
1. the preparation of product
A. 0.1238 ~ 0.3713 g tetraethyl orthosilicate, 0.5655 ~ 1.6965 g Fe (NO3) is accurately taken
39H
2o and 0.2974 ~ 0.8922 g Zn (NO3)
26H
2o, join in 30 ~ 150 mL ethanol-water solutions, ethanol, water volume ratio are 4:1, are stirred to solution transparent;
B. adding 1.5 ~ 2.1 g urea regulator solution pH value to this solution is 6.5 ~ 7.5,50 ~ 70 DEG C of stirring 2 h, cools throw out to room temperature, ageing 4 h.
C. utilize magnetite make its layering and remove supernatant liquid, repeatedly wash solid formation to neutral with distilled water, then use washes of absolute alcohol;
D. by solid formation vacuum-drying to constant weight, 400 ~ 600 DEG C calcining 1 ~ 2 h, obtain silicon magnetic hollow ball ZnSi
0.6fe
1.4o
4.
2. apply
(1) by 25 mg ZnSi
0.6fe
1.4o
4it is in the methyl orange solution of 50 mg/L that hollow ball joins 50 mL concentration, and control pH is about 5.5, ultrasonic disperse 0.5 h, low rate mixing 30 min under natural light, after Magneto separate sedimentation, gets supernatant liquid and measures its ultraviolet-visible absorption spectroscopy.Result shows, the absorption-degradation efficiency of product to tropeolin-D reaches 94.8 %; Effect after recycling for 5 times is not less than 92 %.
(2) by 25 mg ZnSi
0.6fe
1.4o
4it is that in the rhodamine B solution of 50 mg/L, control pH is about 6 that hollow ball joins 50 mL concentration, by the method process of (1).Result shows, the absorption-degradation efficiency of product to rhodamine B reaches 93.6 %; Effect after recycling for 5 times is not less than 91.5 %.
(3) by 25 mg ZnSi
0.6fe
1.4o
4hollow ball join 50 mL concentration be 50 mg/L Acid Red B solution in, control pH is about 6, by the method process of (1).Result shows, the absorption-degradation efficiency of product to Acid Red B reaches 93 %; Effect after recycling for 5 times is not less than 90.5 %.
(4) by 25 mg ZnSi
0.6fe
1.4o
4it is in the methylene blue solution of 50 mg/L that hollow ball joins 50 mL concentration, and control pH is about 6.5, by the method process of (1).Result shows, the absorption-degradation efficiency of product to methylene blue reaches 93.8 %; Effect after recycling for 5 times is not less than 92 %.
(5) by 25 mg ZnSi
0.6fe
1.4o
4it is in the gasoline-water solution of 20 mg/L that hollow ball joins 50 mL concentration, and control pH is 5.0 ~ 6.0, by the method process of (1).Result shows, the absorption-degradation efficiency of product to gasoline reaches 94.2 %; Effect after recycling for 5 times is not less than 91 %.
(6) adopt the method test products identical with upper example to the antibacterial circle diameter of E. Coli, S. Aureus and C. Albicans and minimal inhibitory concentration. result shows, product to the antibacterial circle diameter of E. Coli, S. Aureus and C. Albicans and minimal inhibitory concentration be respectively 33.1,31.6,35.4 mm and 25,25,12.5 μ g/mL.
embodiment 4: silicon magnetic hollow ball ZnSi
0.8
fe
1.2
o
4
1. the preparation of product
A. 0.1651 ~ 0.4952 g tetraethyl orthosilicate, 0.4847 ~ 1.4541 g Fe (NO3) 39H2O and 0.2974 ~ 0.8922 g Zn (NO3) 26H2O is accurately taken, join in 30 ~ 150 mL ethanol-water solutions (ethanol, water volume ratio are 4.5:1), be stirred to solution transparent;
B. adding 1.5 ~ 2.1 g urea regulator solution pH value to this solution is 6.5 ~ 7.5,50 ~ 70 DEG C of stirring 2 h, cools throw out to room temperature, ageing 4 h;
C. utilize magnetite make its layering and remove supernatant liquid, repeatedly wash solid formation to neutral with distilled water, then use washes of absolute alcohol;
D. by solid formation vacuum-drying to constant weight, 400 ~ 600 DEG C calcining 1 ~ 2 h, obtain silicon magnetic hollow ball ZnSi
0.8fe
1.2o
4.
2. apply
(1) by 25 mg ZnSi
0.8fe
1.2o
4it is in the methyl orange solution of 50 mg/L that hollow ball joins 50 mL concentration, and control pH is about 6, ultrasonic disperse 0.5 h, low rate mixing 30 min under natural light, after Magneto separate sedimentation, gets supernatant liquid and measures its ultraviolet-visible absorption spectroscopy.Result shows, the absorption-degradation efficiency of product to tropeolin-D reaches 95.2 %; Effect after recycling for 5 times is not less than 92.5 %.
(2) by 25 mg ZnSi
0.8fe
1.2o
4it is that in the rhodamine B solution of 50 mg/L, control pH is about 6 that hollow ball joins 50 mL concentration, by the method process of (1).Result shows, the absorption-degradation efficiency of product to rhodamine B reaches 92.6 %; Effect after recycling for 5 times is not less than 90.5 %.
(3) by 25 mg ZnSi
0.8fe
1.2o
4it is that in the Acid Red B solution of 50 mg/L, control pH is about 5.5 that hollow ball joins 50 mL concentration, by the method process of (1).Result shows, the absorption-degradation efficiency of product to Acid Red B reaches 92.1 %; Effect after recycling for 5 times is not less than 90 %.
(4) by 25 mg ZnSi
0.8fe
1.2o
4it is in the methylene blue solution of 50 mg/L that hollow ball joins 50 mL concentration, and control pH is about 6.5, by the method process of (1).Result shows, the absorption-degradation efficiency of product to methylene blue reaches 93 %; Effect after recycling for 5 times is not less than 91.5 %.
(5) by 25mg ZnSi
0.8fe
1.2o
4it is that in the machine oil-aqueous solution of 20 mg/L, control pH is about 5.5 that hollow ball joins 50 mL concentration, by the method process of (1).Result shows, the absorption-degradation efficiency of product to machine oil reaches 90.5 %; Effect after recycling for 5 times is not less than 88 %
(6) adopt the method test products identical with upper example to the antibacterial circle diameter of E. Coli, S. Aureus and C. Albicans and minimal inhibitory concentration. result shows, product to the antibacterial circle diameter of E. Coli, S. Aureus and C. Albicans and minimal inhibitory concentration be respectively 33.8,32.4,36.4 mm and 12.5,12.5,6.25 μ g/mL.
embodiment 5: silicon magnetic hollow ball ZnSi
1.0
fe
1.0
o
4
1. the preparation of product
A. 0.2064 ~ 0.6191 g tetraethyl orthosilicate, 0.4039 ~ 1.2117 g Fe (NO3) 39H2O and 0.2974 ~ 0.8922 g Zn (NO3) 26H2O is accurately taken, join in 30 ~ 150 mL ethanol-water solutions (ethanol, water volume ratio are 5:1), be stirred to solution transparent;
B. adding 1.5 ~ 2.1 g urea regulator solution pH value to this solution is 6.5 ~ 7.5,50 ~ 70 DEG C of stirring 2 h, cools throw out to room temperature, ageing 4 h.
C. utilize magnetite make its layering and remove supernatant liquid, repeatedly wash solid formation to neutral with distilled water, then use washes of absolute alcohol;
D. by solid formation vacuum-drying to constant weight, 400 ~ 600 DEG C calcining 1 ~ 2 h, obtain silicon magnetic hollow ball ZnSi
1.0fe
1.0o
4.
2. apply
(1) by 25 mg ZnSi
1.0fe
1.0o
4it is in the methyl orange solution of 50 mg/L that hollow ball joins 50 mL concentration, and control pH is about 6 ~ 7, ultrasonic disperse 0.5 h, low rate mixing 30 min under natural light, after Magneto separate sedimentation, gets supernatant liquid and measures its ultraviolet-visible absorption spectroscopy.Result shows, the absorption-degradation efficiency of product to tropeolin-D reaches 94.6%; Effect after recycling for 5 times is not less than 92 %.
(2) by 25 mg ZnSi
1.0fe
1.0o
4it is that in the rhodamine B solution of 50 mg/L, control pH is about 6 that hollow ball joins 50 mL concentration, by the method process of (1).Result shows, the absorption-degradation efficiency for the treatment of agent to rhodamine B reaches 91.9 %; Effect after recycling for 5 times is not less than 90 %.
(3) by 25 mg ZnSi
1.0fe
1.0o
4it is that in the Acid Red B solution of 50 mg/L, control pH is about 5.5 that hollow ball joins 50 mL concentration, by the method process of (1).Result shows, the absorption-degradation efficiency for the treatment of agent to Acid Red B reaches 91.4 %; Effect after recycling for 5 times is not less than 90 %.
(4) by 25 mg ZnSi
1.0fe
1.0o
4it is in the methylene blue solution of 50 mg/L that hollow ball joins 50 mL concentration, and control pH is about 6.5, by the method process of (1).Result shows, the absorption-degradation efficiency for the treatment of agent to methylene blue reaches 92.4 %; Effect after recycling for 5 times is not less than 91 %.
(5) by 25 mg ZnSi
1.0fe
1.0o
4it is that in the chlorophenol aqueous solution of 20 mg/L, control pH is about 6 that hollow ball joins 50 mL concentration, by the method process of (1).Result shows, the absorption-degradation efficiency of product para-chlorophenol reaches 90.2 %; Effect after recycling for 5 times is not less than 86 %.
(6) adopt the method test products identical with upper example to the antibacterial circle diameter of E. Coli, S. Aureus and C. Albicans and minimal inhibitory concentration.Result shows, product to the antibacterial circle diameter of E. Coli, S. Aureus and C. Albicans and minimal inhibitory concentration be respectively 32.2,30.8,34.6 mm and 25,25,12.5 μ g/mL.
Protection scope of the present invention is not limited only to the technical scheme disclosed in embodiment part, the positive silicon ester of all utilizations, molysite and zinc salt ratio solution, and then adjust ph utilizes CO
2bubble manufactures ZnSi as gas phase template
xfe
2-xo
4the method of hollow ball and the technical scheme of application thereof, all fall into protection scope of the present invention.
Claims (5)
1. silicon magnetic hollow ball ZnSi
xfe
2-xo
4preparation method, it is characterized in that, comprise the steps:
Take positive silicon ester, molysite and zinc salt, the amount of substance of three is than being x:2-x:1 (x=0.2,0.4,0.6,0.8,1.0), and be dissolved in ethanol-water solution, the span of ethanol, water volume ratio is 1:1 ~ 5:1; Be stirred to solution transparent;
Regulator solution pH value is 6.5 ~ 7.5,50 ~ 70 DEG C and stirs 1.5 ~ 2.5 h, is cooled to room temperature, ageing 3.5 ~ 4.5 h;
Remove supernatant liquid to the reaction system layering of step b, distilled water repeatedly washs solid formation to neutral, then use washes of absolute alcohol;
By solids vacuum-drying to constant weight, calcining, obtains silicon magnetic hollow ball ZnSi
xfe
2-xo
4.
2. silicon magnetic hollow ball ZnSi according to claim 1
xfe
2-xo
4preparation method, it is characterized in that: after using the throw out in magnetite absorption reaction system to make itself and solution layering in step c, then remove supernatant liquid.
3. silicon magnetic hollow ball ZnSi according to claim 2
xfe
2-xo
4preparation method, it is characterized in that: positive silicon ester is any one in tetraethoxy, positive silicic acid propyl ester and butyl silicate, and its consumption is 0.2 ~ 3 mmol; Molysite and zinc salt are any one in nitrate, vitriol or muriate etc., and the consumption of molysite is 1 ~ 5.4 mmol, the consumption of zinc salt is 1 ~ 3 mmol; Volume 30 ~ 150 mL of ethanol-distilled water solution, its volume ratio n=1:1 ~ 5:1; The consumption of urea is 1.5 ~ 3.0 g; Calcining temperature is 400 ~ 600 ° of C, and sintering time is 2 ~ 4 h.
4. the silicon magnetic hollow ball ZnSi for preparing of preparation method according to claim 3
xfe
2-xo
4, it is characterized in that: there is process organic pollutant and degerming function; Organic pollutant comprises tropeolin-D, methylene blue, rhodamine B, phenols, kerosene, diesel oil, machine oil; The bacterium that can suppress and kill comprises intestinal bacteria, streptococcus aureus and Candida albicans.
5. the silicon magnetic hollow ball ZnSi prepared by the arbitrary claim of claim 1,2,3,4
xfe
2-xo
4renovation process, it is characterized in that: by use after silicon magnetic hollow ball ZnSi
xfe
2-xo
4be placed in organic solvent or acid-base solution, supersound process 0.5 ~ 1 h, stir 1 ~ 2 h, filter after Magneto separate; Solid matter, through 400 ~ 600 DEG C of calcining 1 ~ 2 h, obtains the product of regeneration, for recycling.
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| JP2003195560A (en) * | 2001-12-27 | 2003-07-09 | Canon Inc | Magnetic toner |
| CN1761003A (en) * | 2005-11-22 | 2006-04-19 | 武汉理工大学 | Method for fabricating magnetic hollow ball |
| CN103043761A (en) * | 2012-12-25 | 2013-04-17 | 常州大学 | Coagulant for algae removal and preparation method thereof |
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| CN103043761A (en) * | 2012-12-25 | 2013-04-17 | 常州大学 | Coagulant for algae removal and preparation method thereof |
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