CN102874758A - 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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- CN102874758A CN102874758A CN201210363048XA CN201210363048A CN102874758A CN 102874758 A CN102874758 A CN 102874758A CN 201210363048X A CN201210363048X A CN 201210363048XA CN 201210363048 A CN201210363048 A CN 201210363048A CN 102874758 A CN102874758 A CN 102874758A
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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 of carbon black planar water solution nano zine oxide preparation, belong to the nano material preparing technical field.
Background technology
In recent years, owing 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 nearly all is the mixture of deriving of nano TiO 2 powder and doping thereof.
Nano zine oxide because have surface effects, quantum size and nontoxic, non-migrating, fluorescence, electroconductibility, in characteristics such as infrared band high emission, as a kind of more potential photocatalyst, the 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 the solid phase method high yield is polluted and lacked, synthesis technique is simply synthetic inhomogeneous, and technological process can't be intervened microtexture effectively.The particle that vapor phase process synthesizes is thinner, but complex process, instrument cost is high, and one-time investment is larger.
Also commonly use at present liquid phase method, the liquid phase method main drawback is that nano-powder all produces reunion, sintering easily at dry, heat treatment stages.Sol-gel method in the liquid phase method, microemulsion method, hydrothermal method, the precipitator method etc., also each existent defect: organic solvent is generally poisonous in the sol-gel method, and the production cycle is long; It is poor that microemulsion method prepares particle dispersion; The 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 just are to overcome the defective of prior art, a kind of method of carbon black planar water solution nano zine oxide preparation is provided, 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, forms 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 of carbon black planar water solution nano zine oxide preparation, described method is: meal zinc oxide is dissolved in the acetum, be mixed into the solvent system that is formed by carbon black-dehydrated alcohol, in mixed solution, slowly drip ammoniacal liquor, regulate the pH value, pour into after the stirring at normal temperature in the reactor, the throw out of reaction gained carbon black absorption gets the high thermal stability nanometer Zinc oxide powder through underpressure distillation, repeatedly washing, dry and calcining.
Concrete preparation method is:
(1) be (5-7) in carbon black and dehydrated alcohol mass ratio: 40 ratio takes by weighing carbon black and dehydrated alcohol, mix and blend, and sonic oscillation 1-2h gets mixed system A;
Be (3-5) in zinc oxide and carbon black mass ratio again: 20 ratio weighing zinc oxide is dissolved in acetum with zinc oxide to 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, regulating the pH value with ammoniacal liquor is 7-10, gets mixed system C;
(3) with mixed system C behind stirring at normal temperature 30-60min, pour in the teflon-lined autoclave, 150 ℃-170 ℃ of temperature, stir 8-14h, be cooled to room temperature, get 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, gets the 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 transfers to mixing solutions with ammoniacal liquor is 8.
Mixed system A and zinc acetate solution B mix, stirring at normal temperature 60min.
The autoclave temperature of reaction is 150 ℃.
In a single day the present invention adds suitable carbon black in zinc acetate and ethanol solution, carbon black is as strong sorbent material, and in autoclave, when temperature reached 150 ℃, zinc acetate was hydrolyzed in solution, forms 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 this moment, carbon black was not oxidized, had 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 was elevated to 600 ℃, carbon black was oxidized, generated finely dispersed ZnO nano powder, had 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, forms 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 that obtains is high, and specific surface area is large, and particle diameter is little, and it is few to reunite, and photocatalysis performance is good.
Description of drawings
Fig. 1 is that specific embodiment 1 gained carbon black adsorption of hydrolyzation legal system gets the TEM figure of zinc oxide precursor behind 600 ℃ of roasting 2h.
Fig. 2 is that specific embodiment 1 gained carbon black adsorption of hydrolyzation legal system gets the XRD figure of zinc oxide precursor behind 600 ℃ of roasting 2h.
Embodiment
Embodiment 1
(1) measure carbon black 2.5g, add in the 20ml dehydrated alcohol, sonic oscillation 1h carries out pre-treatment, gets 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 the 0.1mol/L zinc acetate solution.
(2) the mixed liquid of carbon black is mixed with zinc acetate solution, the pH that slowly drips the ammoniacal liquor regulator solution is 8.
(3) stirring at normal temperature 60min, then pour in the teflon-lined autoclave, at 150 ℃, be cooled to room temperature after stirring 8h, get carbon black adsorption precipitation thing, after repeatedly washing, dry 5h under 80 ℃ condition, 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 the 30ml dehydrated alcohol, sonic oscillation 2h carries out pre-treatment, gets 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 the 0.075mol/L zinc acetate solution.
(2) the mixed liquid of carbon black is mixed with zinc acetate solution, the pH that slowly drips the ammoniacal liquor regulator solution is 7;
(3) stirring at normal temperature 30min, then pour in the teflon-lined autoclave, at 160 ℃, be cooled to room temperature after stirring 10h, get carbon black adsorption precipitation thing warp, after repeatedly washing, dry 3h under 100 ℃ condition, 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 the 40ml dehydrated alcohol, sonic oscillation 1.5h carries out pre-treatment, gets 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 the ammoniacal liquor regulator solution is 9;
(3) stirring at normal temperature 40min, then pour in the teflon-lined autoclave, at 170 ℃, be cooled to room temperature after stirring 12h, get carbon black adsorption precipitation thing warp, after repeatedly washing, dry 3h under 100 ℃ condition, 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 the 40ml dehydrated alcohol, sonic oscillation 2h carries out pre-treatment, gets 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 the 0.1mol/L zinc acetate solution.
(2) the mixed liquid of carbon black is mixed with zinc acetate solution, the pH that slowly drips the ammoniacal liquor regulator solution is 10;
(3) stirring at normal temperature 60min, then pour in the teflon-lined autoclave, at 150 ℃, be cooled to room temperature after stirring 14h, get carbon black adsorption precipitation thing warp, after repeatedly washing, dry 3h under 100 ℃ condition, 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.
In a single day the present invention adds suitable carbon black in reaction solution, as strong sorbent material, form nano particle in the solution, adsorbed by carbon black, has stoped the reunion of ultra-fine grain when precipitation, drying, reduces the sintering in roasting stage.
Effect
The nano zine oxide that the embodiment of the 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 behind 600 ℃ of roasting 2h, about the about 20nm of particle diameter.
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.
It should be noted that at last: obviously, above-described embodiment only is for example of the present invention clearly is described, and is not the 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 need not also can't give all embodiments exhaustive.And the apparent variation of being amplified out thus or change still are among protection scope of the present invention.
Claims (7)
1. the method for carbon black planar water solution nano zine oxide preparation, it is characterized in that, described method is: meal zinc oxide is dissolved in the acetum, be mixed into the solvent system that is formed by carbon black-dehydrated alcohol, in mixed solution, slowly drip ammoniacal liquor, regulate the pH value, pour in the reactor after the stirring at normal temperature, the throw out of reaction gained carbon black absorption gets the high thermal stability nanometer Zinc oxide powder through underpressure distillation, repeatedly washing, dry and calcining.
2. the method for carbon black planar water solution nano zine oxide preparation as claimed in claim 1 is characterized in that, concrete preparation method is:
(1) be (5-7) in carbon black and dehydrated alcohol mass ratio: 40 ratio takes by weighing carbon black and dehydrated alcohol, mix and blend, and sonic oscillation 1-2h gets mixed system A;
Be (3-5) in zinc oxide and carbon black mass ratio again: 20 ratio weighing zinc oxide is dissolved in acetum with zinc oxide to 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, regulating the pH value with ammoniacal liquor is 7-10, gets mixed system C;
(3) with mixed system C behind stirring at normal temperature 30-60min, pour in the teflon-lined autoclave, 150 ℃-170 ℃ of temperature, stir 8-14h, be cooled to room temperature, get 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, gets the high thermal stability nano zine oxide.
3. the method for carbon black planar water solution nano zine oxide preparation as claimed in claim 2 is characterized in that the concentration of acetum is 1 mol/L.
4. the method for carbon black planar water solution nano zine oxide preparation as claimed in claim 3 is characterized in that the mass concentration of ammoniacal liquor is 35%.
5. the method for carbon black planar water solution nano zine oxide preparation as claimed in claim 4 is characterized in that the pH value that transfers to mixing solutions with ammoniacal liquor is 8.
6. the method for carbon black planar water solution nano zine oxide preparation as claimed in claim 5 is characterized in that, mixed system A and zinc acetate solution B mix, stirring at normal temperature 60min.
7. the method for carbon black planar water solution nano zine oxide preparation as claimed in claim 6 is characterized in that the autoclave temperature of reaction is 150 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110801810A (en) * | 2019-11-19 | 2020-02-18 | 哈尔滨工业大学 | Preparation method of molecular pollution adsorption material with ZnO film coated with carbon black and adsorption device |
| CN111052468A (en) * | 2017-09-19 | 2020-04-21 | 电化株式会社 | Carbon black for battery, coating liquid for battery, positive electrode for nonaqueous battery, and nonaqueous battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111052468A (en) * | 2017-09-19 | 2020-04-21 | 电化株式会社 | Carbon black for battery, coating liquid for battery, positive electrode for nonaqueous battery, and nonaqueous battery |
| CN111052468B (en) * | 2017-09-19 | 2022-09-16 | 电化株式会社 | Carbon black for battery, coating liquid for battery, positive electrode for nonaqueous battery, and nonaqueous battery |
| US11658278B2 (en) | 2017-09-19 | 2023-05-23 | Denka Company Limited | Carbon black for batteries, coating liquid for batteries, positive electrode for nonaqueous batteries and nonaqueous battery |
| CN110801810A (en) * | 2019-11-19 | 2020-02-18 | 哈尔滨工业大学 | Preparation method of molecular pollution adsorption material with ZnO film coated with carbon black and adsorption device |
| 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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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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