CN102863791A - Preparation method of zinc-oxide/polyaniline composite hollow microsphere - Google Patents
Preparation method of zinc-oxide/polyaniline composite hollow microsphere Download PDFInfo
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- CN102863791A CN102863791A CN2012102439279A CN201210243927A CN102863791A CN 102863791 A CN102863791 A CN 102863791A CN 2012102439279 A CN2012102439279 A CN 2012102439279A CN 201210243927 A CN201210243927 A CN 201210243927A CN 102863791 A CN102863791 A CN 102863791A
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Abstract
The invention relates to a preparation method of a zinc-oxide/polyaniline composite hollow microsphere, belonging to the technical field of inorganic-organic composite function material preparation. The important contents of the invention are mainly that: zinc salt and aniline monomer are adopted as raw materials, a ZnO/PANI composite material with a hollow microsphere structure is formed by one-step reaction and self assembly simultaneously; and the prepared ZnO/PANI composite material has the characteristics of uniform particle distribution and close interfacial bonding, the ZnO and the PANI show good synergistic gain action, the ZnO/PANI composite material has a special hollow microsphere structure and has wide application prospect in the aspects of photoelectric devices, biosensors, chemical sensors and the like. The method has the advantages that the price of the raw materials is low, the needed equipment is simple, the process condition is mild and easy and is convenient to control, and the practical large-scale production potential is achieved.
Description
Technical field
The present invention relates to the preparation method of a kind of zinc oxide/polyaniline compound hollow microballoon, belong to inorganic-organic hybrid functional materials preparing technical field.
Background technology
Combination on nanoscale forms inorganic-organic nanocomposite by inorganic phase and organic phase, has the workability of organic materials and the functional and constructional feature of inorganic materials concurrently.The existence of organic phase can prevent the gathering of inorganic particulate and keep the good spatial distribution of particulate, can solve the problem that inorganic nano-particle is easily reunited, and in various degree existence Physicochemical interaction between the inorganic-organic two-phase interface, make matrix material be not only the bi-material function simply adding and, often show good cooperative gain effect, give material new function.
Zinc oxide/polyaniline (ZnO/PANI) nano composite material since separately superior performance be subject to domestic and international researchist's extensive concern, to solve separately weak point in actual applications.ZnO/PANI is with a wide range of applications in a plurality of fields, significantly strengthen the ultraviolet light emission intensity of ZnO with the recombination energy of PANI, improve the bio-compatibility of ZnO, significantly improve photoelectric transformation efficiency, can be used as the critical material of photoelectric device, biosensor, chemical sensor etc.But ZnO/PANI goes back some problems of ubiquity in actual applications, such as ZnO Nanoparticles skewness, interface performance are difficult to control etc.The existence of these problems has limited the application prospect of ZnO/PANI.
Exist the major cause of these problems and the preparation method of ZnO/PANI nano composite material that direct relation is arranged.Report according to present domestic and foreign literature, the preparation of ZnO/PANI nano composite material mainly contains following two kinds of methods, a kind of is the nanostructure for preparing respectively bi-material, then by the method for solution chemistry they is mixed or directly carries out simple mechanically mixing; Another kind is to prepare in advance the ZnO with nanostructure, and it is processed into finely disseminated suspension, then carries out the in-situ polymerization of aniline monomer in the presence of nano-ZnO.Before a kind of method often bi-material simply add and, the cooperative gain effect that is difficult to show bi-material; Rear a kind of method often can not get having the polyaniline of nanostructure, is not nano composite material truly.
Summary of the invention
The ZnO/PANI matrix material ZnO size distribution that the object of the invention is to overcome existing method preparation is inhomogeneous, the interface in conjunction with not closely, the uncontrollable shortcoming of composite nanostructure, adopt single step reaction method self-assembled growth to form and have the hollow nanostructured ZnO/PANI matrix material of nucleocapsid, propose a kind of novel method for preparing zinc oxide/polyaniline compound hollow microballoon.
The preparation method of a kind of zinc oxide of the present invention/polyaniline compound hollow microballoon is characterized in that having following preparation process and step:
(1) with aniline 100 ~ 120 ℃ of lower underpressure distillation 2 times;
(2) aqueous solution of preparation zinc salt adds distilled aniline in the zinc solution ultra-sonic dispersion 15 minutes; The consumption of aniline and zinc, both mol ratios are (0.2 ~ 1.2): 1;
(3) the preparation alkaline solution joins in the mentioned solution, stirs 30 minutes; The consumption of alkali is 4 ~ 12 times of zinc salt mole number;
(4) aqueous solution of preparation ammonium persulphate joins the aqueous solution of ammonium persulphate in the mentioned solution, stirs after 1 ~ 2 minute under room temperature (10 ~ 25 ℃) standing and reacting 1 ~ 2 hour; The consumption of ammonium persulphate is 0.8 ~ 1.2 times of aniline mole number;
(5) after the container sealing with the splendid attire said mixture, under 80 ~ 90 ℃, continued standing and reacting 24 ~ 48 hours;
(6) cooling, suction filtration, water and ethanol repetitive scrubbing filter cake namely get the ZnO/PANI mixture after the drying.
Described zinc salt is any one in zinc acetate, zinc chloride, the zinc nitrate salt; Described alkali is any one in sodium hydroxide, potassium hydroxide, lithium hydroxide, the ammoniacal liquor.
Relevant mechanism of the present invention or principle: in preparation process of the present invention, because aniline is not almost allowed in neutral or slightly acidic zinc salt solution, aniline monomer forms fine droplet in zinc salt solution.After adding alkali lye, formed ZnO precursor compound forms the hollow ball shape structural material at the surface aggregation of drop.After adding ammonium persulphate, the aniline monomer that table coats is filled in the inside of coccoid or is attached to internal surface from internal surface in the bulb interior polymerization.The ZnO precursor compound issues the reaction of unboiled water solution in higher temperature, forms the ZnO shell of nanostructure.In the present invention, the aniline monomer fine droplet forms the soft template of spherical housing as the ZnO precursor compound, and the aniline oligomer forms the micro-nano-sphere with ZnO/PANI shell/nuclear hollow structure as the template of ZnO precursor compound hydrolysis reaction simultaneously.System one step concerted reaction self-assembly forms simultaneously because ZnO/PANI is compound, therefore have even particle distribution, the compact characteristics in interface, thereby improve thermostability, dimensional stability and the photoelectric properties etc. of ZnO/PANI mixture, both have good cooperative gain effect.
Polymerization process among the present invention is the out-phase forming core, and polyaniline carries out polymerization take the ZnO precursor as nuclear.
ZnO involved in the present invention is obtained through hydrolysis by zinc salt and the formed precursor of alkali.
Advantage of the present invention and characteristics
It is raw material that the present invention adopts zinc salt and aniline monomer, and step concerted reaction self-assembly forms the ZnO/PANI matrix material with tiny balloon structure simultaneously.Cost of material is cheap, and required equipment is simple, and the control of easily acting charitably of processing condition gentleness has the practical application potentiality.
The present invention has overcome existing ZnO/PANI matrix material need prepare the two-step reaction preparation process that nano zine oxide carries out aniline polymerization more in advance, and compare with the prepared ZnO/PANI matrix material of current methods, have even particle distribution, the compact characteristics in interface, both show good cooperative gain effect at aspects such as thermostability, photovoltaic effect, and have special tiny balloon structure.
Embodiment
After now specific embodiments of the invention being described in.
Preparation process and the step of the present embodiment are as follows:
(1) with aniline 110 ℃ of lower underpressure distillation 2 times;
(2) take by weighing Zinc diacetate dihydrate 2.20 grams, be dissolved in the 20mL water, add aniline 1mL, ultra-sonic dispersion 15 minutes;
(3) weighing sodium hydroxide 3.2 grams are dissolved in the 20mL water, and alkaline solution is poured in the mentioned solution, stir 30 minutes;
(4) take by weighing ammonium persulphate 2.5 gram, be dissolved in the 10mL water, pour in the mentioned solution, rapid stirring after 1 ~ 2 minute under room temperature (18 ℃) standing and reacting 1 ~ 2 hour;
(5) after the container sealing with the splendid attire said mixture, under 80 ℃, continued standing and reacting 24 hours;
(6) cooling, suction filtration, water and ethanol repetitive scrubbing filter cake namely get the ZnO/PANI mixture after the drying.
Preparation process and the step of the present embodiment are as follows:
(1) with aniline 110 ℃ of lower underpressure distillation 2 times;
(2) take by weighing Zinc diacetate dihydrate 2.20 grams, be dissolved in the 20mL water, add aniline 0.5mL, ultra-sonic dispersion 15 minutes;
(3) weighing sodium hydroxide 3.2 grams are dissolved in the 20mL water, and alkaline solution is poured in the mentioned solution, stir 30 minutes;
(4) take by weighing ammonium persulphate 1.25 gram, be dissolved in the 10mL water, pour in the mentioned solution, rapid stirring after 1 ~ 2 minute under room temperature standing and reacting 1 ~ 2 hour;
(5) after the container sealing with the splendid attire said mixture, under 80 ℃, continued standing and reacting 24 hours;
(6) cooling, suction filtration, water and ethanol repetitive scrubbing filter cake namely get the ZnO/PANI mixture after the drying.
Embodiment 3
Preparation process and the step of the present embodiment are as follows:
(1) with aniline 110 ℃ of lower underpressure distillation 2 times;
(2) take by weighing zinc nitrate hexahydrate 3.0 grams, be dissolved in the 20mL water, add aniline 1mL, ultra-sonic dispersion 15 minutes;
(3) measure 30% ammonia soln 10mL, other adds 10 mL water, and alkaline solution is poured in the mentioned solution, stirs 30 minutes;
(4) take by weighing ammonium persulphate 2.5 gram, be dissolved in the 10mL water, pour in the mentioned solution, rapid stirring after 1 ~ 2 minute under room temperature standing and reacting 1 ~ 2 hour;
(5) after the container sealing with the splendid attire said mixture, under 80 ℃, continued standing and reacting 24 hours;
(6) cooling, suction filtration, water and ethanol repetitive scrubbing filter cake namely get the ZnO/PANI mixture after the drying.
The sign of the prepared zinc oxide of the present invention/polyaniline compound hollow microballoon with identify the method that adopts scanning electronic microscope (SEM), XRD powdery diffractometry and pressing potassium bromide troche FTIR, the instrument of use is respectively the QUANTA200 of U.S. FEI Co. type scanning electronic microscope, Rigaku company's T TR III type turns target X-ray diffractometer and U.S. Thermo Nicolet FT-IR AVATAR 3600 type infrared spectrometers.The detected result of embodiment 1 prepared sample is seen Figure of description.
Description of drawings: accompanying drawing 1 is the SEM photo of embodiment 1 prepared sample, and accompanying drawing 2 is the XRD powder diffraction spectrum of embodiment 1 prepared sample, and accompanying drawing 3 is the FTIR collection of illustrative plates of embodiment 1 prepared sample.
Claims (3)
1. the preparation method of a kind of zinc oxide of the present invention/polyaniline compound hollow microballoon is characterized in that having following preparation process and step:
(1) with aniline 100 ~ 120 ℃ of lower underpressure distillation 2 times;
(2) aqueous solution of configuration zinc salt adds distilled aniline in the zinc solution ultra-sonic dispersion 15 minutes; The consumption of aniline and zinc, both mol ratios are (0.1 ~ 1): 1;
(3) the preparation alkaline solution joins in the mentioned solution, stirs 30 minutes; The consumption of alkali is 4 ~ 12 times of zinc salt mole number;
(4) aqueous solution of preparation ammonium persulphate joins the aqueous solution of ammonium persulphate in the mentioned solution, stirs after 1 ~ 2 minute under room temperature (10 ~ 25 ℃) standing and reacting 1 ~ 2 hour; The consumption of ammonium persulphate is 0.8 ~ 1.2 times of aniline mole number;
(5) after the container sealing with the splendid attire said mixture, under 80 ~ 90 ℃, continued standing and reacting 24 ~ 48 hours;
(6) cooling, suction filtration, water and ethanol repetitive scrubbing filter cake namely get the ZnO/PANI mixture after the drying.
2. the preparation method of a kind of zinc oxide/polyaniline compound hollow microballoon as claimed in claim 1 is characterized in that described zinc salt is zinc acetate, zinc chloride, zinc nitrate; Described alkali is sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor.
3. the preparation method of a kind of zinc oxide/polyaniline compound hollow microballoon as claimed in claim 1 is characterized in that described alkali add-on take zinc salt as benchmark, and both mol ratios are (4 ~ 12): 1; Described ammonium persulphate add-on is take aniline as benchmark, and both mol ratios are (0.8 ~ 1.2): 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102783500A (en) * | 2012-08-21 | 2012-11-21 | 昆明理工大学 | Nano polyaniline/ZnO composite antibacterial agent and preparation method thereof |
| CN104163745A (en) * | 2013-05-20 | 2014-11-26 | 湖北航天化学技术研究所 | Assistant agent for reducing impact sensitivity of mixed nitrate/nitramine propellant, and application thereof |
| CN104492490A (en) * | 2014-12-01 | 2015-04-08 | 常州大学 | Zinc oxide-polyaniline composite photocatalytic material with efficient photocatalytic activity and preparation method of zinc oxide-polyaniline composite photocatalyst material |
| CN114011462A (en) * | 2021-11-18 | 2022-02-08 | 扬州大学 | Polyaniline loaded zinc catalyst and preparation method and application thereof |
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| CN1718612A (en) * | 2005-07-14 | 2006-01-11 | 西南师范大学 | Inorganic oxide conductive powder/polyaniline conductive polymer composite material and its preparation method |
| CN101885915A (en) * | 2010-08-11 | 2010-11-17 | 哈尔滨工业大学 | Method for preparing magnetic ferroferric oxide/conductive polyaniline light-weight composite hollow microspheres |
| CN102134326A (en) * | 2010-11-08 | 2011-07-27 | 上海大学 | Preparation method of polyaniline/zinc oxide flexible composite electrode material |
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2012
- 2012-07-16 CN CN2012102439279A patent/CN102863791A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1718612A (en) * | 2005-07-14 | 2006-01-11 | 西南师范大学 | Inorganic oxide conductive powder/polyaniline conductive polymer composite material and its preparation method |
| CN101885915A (en) * | 2010-08-11 | 2010-11-17 | 哈尔滨工业大学 | Method for preparing magnetic ferroferric oxide/conductive polyaniline light-weight composite hollow microspheres |
| CN102134326A (en) * | 2010-11-08 | 2011-07-27 | 上海大学 | Preparation method of polyaniline/zinc oxide flexible composite electrode material |
Non-Patent Citations (2)
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| JAUDER JENG,ET AL.: "Growth mechanism and pH-regulation characteristics of composite latex particles prepared from Pickering emulsion polymerization of aniline/ZnO using different hydrophilicities of oil phases", 《POLYMER》 * |
| YONGJUN HE: "Preparation of polyaniline/nano-ZnO composites via a novel Pickering emulsion route", 《POWDER TECHNOLOGY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102783500A (en) * | 2012-08-21 | 2012-11-21 | 昆明理工大学 | Nano polyaniline/ZnO composite antibacterial agent and preparation method thereof |
| CN102783500B (en) * | 2012-08-21 | 2014-08-06 | 昆明理工大学 | Nano polyaniline/ZnO composite antibacterial agent and preparation method thereof |
| CN104163745A (en) * | 2013-05-20 | 2014-11-26 | 湖北航天化学技术研究所 | Assistant agent for reducing impact sensitivity of mixed nitrate/nitramine propellant, and application thereof |
| CN104492490A (en) * | 2014-12-01 | 2015-04-08 | 常州大学 | Zinc oxide-polyaniline composite photocatalytic material with efficient photocatalytic activity and preparation method of zinc oxide-polyaniline composite photocatalyst material |
| CN114011462A (en) * | 2021-11-18 | 2022-02-08 | 扬州大学 | Polyaniline loaded zinc catalyst and preparation method and application thereof |
| CN114011462B (en) * | 2021-11-18 | 2023-10-27 | 扬州大学 | Polyaniline loaded zinc catalyst and preparation method and application thereof |
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