CN102874758B - Method for preparing nano zinc oxide by carbon black adsorption hydrolysis - Google Patents
Method for preparing nano zinc oxide by carbon black adsorption hydrolysis Download PDFInfo
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- CN102874758B CN102874758B CN201210363048.XA CN201210363048A CN102874758B CN 102874758 B CN102874758 B CN 102874758B CN 201210363048 A CN201210363048 A CN 201210363048A CN 102874758 B CN102874758 B CN 102874758B
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Abstract
The invention discloses a method for preparing nano zinc oxide by a carbon black adsorption hydrolysis. The method comprises the following steps of: dissolving zinc oxide crude powder in an acetic acid solution, and mixing the mixture in a solvent system which consists of carbon black-absolute ethanol; dripping ammonia water into the mixed solution slowly, regulating the pH value, stirring at normal temperature and pouring into a reaction kettle; and distilling a precipitate adsorbed by carbon black in the reaction process under reduced pressure, washing for multiple times, drying and calcining to obtain high-heat stability nano zinc oxide powder. According to the method, on the basis of the ordinary precipitation method, the carbon black is used as an adsorbent, the agglomeration and sintering of zinc oxide ultrafine particles in the stages of drying and heat treatment are reduced, so that the method has the characteristics of simple process, convenience for operation and high yield; and the obtained product is high in degree of crystallinity, large in specific surface area, small in grain diameter, little in agglomeration and high in photocatalytic performance.
Description
Technical field
The present invention relates to a kind of method prepared by carbon black planar water solution nano zine oxide, belong to nano material preparing technical field.
Background technology
In recent years, due to the widespread use of photocatalysis technology in daily life, for example organic and inorganic wastewater treatment, purifying air, the researchs such as ultraviolet laser, therefore many investigators have proposed the synthetic preparation about nano-photocatalyst.Existing photocatalyst is nearly all the derivative mixture of nano TiO 2 powder and doping thereof.
Nano zine oxide because there is surface effects, quantum size and nontoxic, non-migrating, fluorescence, electroconductibility, in features such as infrared band high emission, as a kind of more potential photocatalyst, nanometer Zinc oxide powder report also increases gradually.
As photocatalyst, need in preparation process, form certain crystalline structure, to improve its photocatalysis performance.In existing various preparation methods, although solid phase method high yield is polluted less, synthesis technique is simply synthetic inhomogeneous, and technological process cannot be intervened microtexture effectively.The synthetic particle of vapor phase process is thinner, but complex process, instrument cost is high, and one-time investment is larger.
Also commonly use at present liquid phase method, liquid phase method main drawback is that nano-powder all easily produces reunion, sintering at dry, heat treatment stages.Sol-gel method in liquid phase method, microemulsion method, hydrothermal method, the precipitator method etc., also each existent defect: in sol-gel method, organic solvent is generally poisonous, and the production cycle is long; It is poor that microemulsion method is prepared particle dispersion; Hydrothermal method particle is uniformly dispersed but particle diameter is larger; Precipitator method reaction is inhomogeneous, and reaction process is difficult to control.
Summary of the invention
The technical issues that need to address of the present invention are just to overcome the defect of prior art, a kind of method that provides carbon black planar water solution nano zine oxide to prepare, it is on common precipitator method basis, utilize carbon black as sorbent material, reduced reunion and the sintering of zinc oxide ultra-fine particle at dry and heat treatment stages, thereby the particle diameter that makes synthetic nanoparticle is less, uniform particles, crystal formation are good, form the large super fine zinc oxide nano-powder of specific surface area.
For addressing the above problem, the present invention adopts following technical scheme:
The invention provides a kind of method prepared by carbon black planar water solution nano zine oxide, described method is: meal zinc oxide is dissolved in acetum, be mixed into the solvent system being formed by carbon black-dehydrated alcohol, in mixed solution, slowly drip ammoniacal liquor, regulate pH value, after stirring at normal temperature, pour in reactor, the throw out of reaction gained carbon black absorption through underpressure distillation, repeatedly wash, dry and calcining, obtain high thermal stability nanometer Zinc oxide powder.
Concrete preparation method is:
(1) in carbon black and dehydrated alcohol mass ratio, be (5-7): 40 ratio takes carbon black and dehydrated alcohol, mix and blend, sonic oscillation 1-2h, obtains mixed system A;
In zinc oxide and carbon black mass ratio, be (3-5) again: 20 ratio weighs zinc oxide, zinc oxide is dissolved in to acetum be configured to the zinc acetate solution B that concentration is 0.05-0.1mol/L;
(2) at normal temperatures, mixed system A and zinc acetate solution B are mixed, stir 30-60min, with ammoniacal liquor, regulating pH value is 7-10, obtains mixed system C;
(3) by mixed system C after stirring at normal temperature 30-60min, pour in teflon-lined autoclave, 150 ℃-170 ℃ of temperature, stir 8-14h, be cooled to room temperature, obtain carbon black adsorption precipitation thing, through repeatedly washing, again drying and grind after, heat-up rate with 10-20 ℃/min is warming up to 500-800 ℃ of roasting 2-4h, obtains high thermal stability nano zine oxide.
The concentration of acetum is 1 mol/L.
The mass concentration of ammoniacal liquor is 35%.
The pH value that is adjusted to mixing solutions with ammoniacal liquor is 8.
Mixed system A and zinc acetate solution B mix, stirring at normal temperature 60min.
Autoclave temperature of reaction is 150 ℃.
The present invention adds suitable carbon black in zinc acetate and ethanol solution, and carbon black is as strong sorbent material, and in autoclave, when temperature reaches 150 ℃, zinc acetate is hydrolyzed in solution, once form Zn (OH) in reaction process
2precipitation, is adsorbed by carbon black, forms the nanometer Zn (OH) of carbon black absorption
2system, stops Zn (OH)
2precipitation continues to grow up; In roasting process, when temperature is elevated to 400 ℃, the Zn (OH) of carbon black absorption
2dehydration, forms carbon black absorption ZnO nano powder gradually, and now carbon black is not oxidized, has prevented the reunion of ZnO nano powder; When temperature was elevated to before 500 ℃, carbon black is also not oxidized, further stops the sintering of ZnO nano powder; When temperature is elevated to 600 ℃, carbon black is oxidized, generates finely dispersed ZnO nano powder, has reduced the sintering of ZnO nano powder under hot conditions.
Thereby, the present invention adopts carbon black planar water solution, on common precipitator method basis, utilize carbon black as sorbent material, reduced reunion and the sintering of zinc oxide ultra-fine particle at dry and heat treatment stages, thereby the particle diameter that makes synthetic nanoparticle is less, uniform particles, crystal formation are good, form the large super fine zinc oxide nano-powder of specific surface area.
Technique of the present invention is simple, easy and simple to handle, productive rate is high, and the product degree of crystallinity obtaining is high, and specific surface area is large, and particle diameter is little, reunites few, and photocatalysis performance is good.
Accompanying drawing explanation
Fig. 1 is that specific embodiment 1 gained carbon black adsorption of hydrolyzation legal system obtains the TEM figure of zinc oxide precursor after 600 ℃ of roasting 2h.
Fig. 2 is that specific embodiment 1 gained carbon black adsorption of hydrolyzation legal system obtains the XRD figure of zinc oxide precursor after 600 ℃ of roasting 2h.
Embodiment
embodiment 1
(1) measure carbon black 2.5g, add in 20ml dehydrated alcohol, sonic oscillation 1h carries out pre-treatment, obtains the mixed liquid of carbon black;
Measure meal zinc oxide 0.5g again, be dissolved in the acetum of 1mol/L, being made into 60ml concentration is 0.1mol/L zinc acetate solution.
(2) the mixed liquid of carbon black is mixed with zinc acetate solution, the pH that slowly drips ammoniacal liquor regulator solution is 8.
(3) stirring at normal temperature 60min, then pour in teflon-lined autoclave, at 150 ℃, after stirring 8h, be cooled to room temperature, obtain carbon black adsorption precipitation thing, after repeatedly washing, dry 5h under the condition of 80 ℃, heat-up rate with 10 ℃/min after grinding is warming up to 600 ℃ of roasting 2h, makes the Zinc oxide powder of the about 20nm of particle diameter.
embodiment 2
(1) measure carbon black 6g, add in 30ml dehydrated alcohol, sonic oscillation 2h carries out pre-treatment, obtains the mixed liquid of carbon black; Measure meal zinc oxide 0.9g again, be dissolved in the acetum of 1mol/L, being made into 150ml concentration is 0.075mol/L zinc acetate solution.
(2) the mixed liquid of carbon black is mixed with zinc acetate solution, the pH that slowly drips ammoniacal liquor regulator solution is 7;
(3) stirring at normal temperature 30min, then pour in teflon-lined autoclave, at 160 ℃, after stirring 10h, be cooled to room temperature, obtain carbon black adsorption precipitation thing warp, repeatedly, after washing, under the condition of 100 ℃, be dried 3h, heat-up rate with 15 ℃/min after grinding is warming up to 500 ℃ of roasting 4h, makes the Zinc oxide powder of the about 28nm of particle diameter.
embodiment 3
(1) measure carbon black 5g, add in 40ml dehydrated alcohol, sonic oscillation 1.5h carries out pre-treatment, obtains the mixed liquid of carbon black; Measure meal zinc oxide 0.125g again, be dissolved in the acetum of 1mol/L, being made into concentration is 0.09 mol/L zinc acetate solution.
(2) the mixed liquid of carbon black is mixed with zinc acetate solution, the pH that slowly drips ammoniacal liquor regulator solution is 9;
(3) stirring at normal temperature 40min, then pour in teflon-lined autoclave, at 170 ℃, after stirring 12h, be cooled to room temperature, obtain carbon black adsorption precipitation thing warp, repeatedly, after washing, under the condition of 100 ℃, be dried 3h, heat-up rate with 20 ℃/min after grinding is warming up to 700 ℃ of roasting 4h, makes the Zinc oxide powder of the about 25nm of particle diameter.
embodiment 4
(1) measure carbon black 7g, add in 40ml dehydrated alcohol, sonic oscillation 2h carries out pre-treatment, obtains the mixed liquid of carbon black; Measure meal zinc oxide 0.175g again, be dissolved in the acetum of 1mol/L, being made into concentration is 0.1mol/L zinc acetate solution.
(2) the mixed liquid of carbon black is mixed with zinc acetate solution, the pH that slowly drips ammoniacal liquor regulator solution is 10;
(3) stirring at normal temperature 60min, then pour in teflon-lined autoclave, at 150 ℃, after stirring 14h, be cooled to room temperature, obtain carbon black adsorption precipitation thing warp, repeatedly, after washing, under the condition of 100 ℃, be dried 3h, heat-up rate with 10 ℃/min after grinding is warming up to 800 ℃ of roasting 4h, makes the Zinc oxide powder of the about 35nm of particle diameter.
The present invention adds suitable carbon black in reaction solution, as strong sorbent material, once form nano particle in solution, by carbon black, is adsorbed, and has stoped the reunion of ultra-fine grain when precipitating, being dried, and reduces the sintering in roasting stage.
effect
The nano zine oxide that the embodiment of the present invention 1 makes, as seen from Figure 1, Figure 2, the carbon black absorbing high temp precipitator method make the zinc oxide nano-powder that zinc oxide precursor obtains after 600 ℃ of roasting 2h, the about 20nm of particle diameter left and right.
The nano zine oxide that the present invention makes, degree of crystallinity is high, and specific surface area is large, and particle diameter is little, adopts carbon black absorption method production cost low, is convenient to carry out the production of extensive nano zine oxide.
Finally it should be noted that: obviously, above-described embodiment is only for example of the present invention is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments.And the apparent variation of being amplified out thus or change are still among protection scope of the present invention.
Claims (1)
1. the method that prepared by carbon black planar water solution nano zine oxide, is characterized in that, described method is:
(1) measure carbon black 2.5g, add in 20ml dehydrated alcohol, sonic oscillation 1h carries out pre-treatment, obtains the mixed liquid of carbon black;
Measure meal zinc oxide 0.5g again, be dissolved in the acetum of 1mol/L, being made into 60ml concentration is 0.1mol/L zinc acetate solution;
(2) the mixed liquid of carbon black is mixed with zinc acetate solution, the pH that slowly drips ammoniacal liquor regulator solution is 8;
(3) stirring at normal temperature 60min, then pour in teflon-lined autoclave, at 150 ℃, after stirring 8h, be cooled to room temperature, obtain carbon black adsorption precipitation thing, after repeatedly washing, dry 5h under the condition of 80 ℃, heat-up rate with 10 ℃/min after grinding is warming up to 600 ℃ of roasting 2h, makes the Zinc oxide powder of particle diameter 20nm.
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| CN110801810B (en) * | 2019-11-19 | 2020-10-16 | 哈尔滨工业大学 | Preparation method of molecular pollution adsorption material with ZnO film coated with carbon black and adsorption device |
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| CN101182030A (en) * | 2007-11-27 | 2008-05-21 | 华东师范大学 | ZnO nano strip material and preparation method thereof |
| CN102432065A (en) * | 2011-09-07 | 2012-05-02 | 内蒙古科技大学 | Method for synthesizing nanometer titanium dioxide through using carbon to adsorb titanium tetrachloride hydrolysis system |
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| CN101182030A (en) * | 2007-11-27 | 2008-05-21 | 华东师范大学 | ZnO nano strip material and preparation method thereof |
| CN102432065A (en) * | 2011-09-07 | 2012-05-02 | 内蒙古科技大学 | Method for synthesizing nanometer titanium dioxide through using carbon to adsorb titanium tetrachloride hydrolysis system |
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Inventor after: Guo Guibao Inventor after: Hao Yan Inventor after: An Shengli Inventor after: Ma Xuelian Inventor after: Jie Ruihua Inventor before: Guo Guibao Inventor before: Ma Xuelian Inventor before: An Shengli Inventor before: Jie Ruihua |
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