CN102206356B - Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles and preparation method thereof - Google Patents
Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles and preparation method thereof Download PDFInfo
- Publication number
- CN102206356B CN102206356B CN201110080358A CN201110080358A CN102206356B CN 102206356 B CN102206356 B CN 102206356B CN 201110080358 A CN201110080358 A CN 201110080358A CN 201110080358 A CN201110080358 A CN 201110080358A CN 102206356 B CN102206356 B CN 102206356B
- Authority
- CN
- China
- Prior art keywords
- polystyrene
- noble metal
- particle
- metal nano
- polyaniline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 90
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 77
- 239000011246 composite particle Substances 0.000 title claims abstract description 42
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010970 precious metal Substances 0.000 title abstract 5
- 239000002245 particle Substances 0.000 claims abstract description 91
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000839 emulsion Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 claims description 49
- 239000002082 metal nanoparticle Substances 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 19
- 239000010931 gold Substances 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000011324 bead Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 4
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000005457 ice water Substances 0.000 description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 235000013339 cereals Nutrition 0.000 description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- 239000004005 microsphere Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QLSWIGRIBOSFMV-UHFFFAOYSA-N 1h-pyrrol-2-amine Chemical class NC1=CC=CN1 QLSWIGRIBOSFMV-UHFFFAOYSA-N 0.000 description 1
- FCMUPMSEVHVOSE-UHFFFAOYSA-N 2,3-bis(ethenyl)pyridine Chemical compound C=CC1=CC=CN=C1C=C FCMUPMSEVHVOSE-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- OIRDTQYFTABQOQ-UHTZMRCNSA-N Vidarabine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@@H]1O OIRDTQYFTABQOQ-UHTZMRCNSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 210000000617 arm Anatomy 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention provides a polystyrene/ polyaniline/ precious metal nanoparticle composite particle and a preparation method thereof. The composite particle has such a structure that the surface of a polystyrene particle is covered with a casing layer and precious metal nanoparticles are embeded into the casing layer and the surface. The preparation method of the composite particles comprises the steps of dispersing aniline in water through stirring and ultrasonic processing at a temperature below zero and mixing the dispersion and polystyrene emulsion to produce a reaction; after the reaction of the above mixture lasts for a certain time, adding orderly precious metal nanoparticle sol, ammonium persulfate aqueous solution and hydrochloric acid into the reaction products, wherein the hydrochloric acid is added dropwisely into reaction products and the mixture undergoes a reaction for 4 hours; then heating the reaction products to room temperature and making the reaction products undergo a continued reaction for 20 hours; carrying out filtering separation, washing and drying to obtain powdery polystyrene/ polyaniline/ precious metal nanoparticle composite particles.
Description
Technical field
The invention belongs to the nano-functional material technical field, be specifically related to a kind of polystyrene/polyaniline/noble metal nano particles composite particles and preparation method thereof and preparation method thereof.
Technical background
Conductive polymers latex nano-complex particle material integrates electroconductibility and nano particle functional of polymer self, and having molecular structure can design, advantages such as specific conductivity adjustable and morphological specificity may command.Noble metal nano particles such as gold have unique optical property and good chemicalstability; Has the PS/noble metal nano composite particles of " Fried Glutinous Rice Balls with Sesame " type structure owing to have very superior catalysis, electricity and optical property; Particularly they absorb at the controlled surface plasma body resonant vibration of aqueous phase, all have broad application prospects at numerous areas such as electronics and optics, chemistry and biology transmitter, catalyzer and medical imagings.Noble metal nano particles is introduced conductive polymers latex nano-complex particle; Not only can strengthen the combination stability between noble metal nano particles and the substrate; Eliminate its dissipation to environment; Thereby improve its work-ing life and increase its life cycle, and also be significantly improved for performances such as the catalysis of particle itself, sensings.Secondly; To its functional performance and practical application; The yardstick of noble metal nano particles and controllability thereof are one of very important characteristics, as people such as J.C.Meredith preparation and and then studied influence (reference 1:Chemistry of Materials, 2009 of golden nanometer particle yardstick to ultraviolet light response wavelength moving characteristic; 21,5654-5663).And when using as catalyzer, then hope noble metal nano particles in this type composite particles reach finer yardstick (reference 2:Angewandte Chemie International Edition, 2007,46,4151-4154).Therefore, the controllability of raising noble metal nano particles is very important in a composite particles technology of preparing aspect.
Is the composite particles with polymkeric substance-conducting polymer-noble metal nano particles three components of matrix (like PS) for preparation with common polymer; Mangeney proposes a kind of method of static self-assembly: adopt pyrroles and amino-pyrroles surface and copolymerized at polystyrene microsphere; Prepare the surface and be rich in amido modified PS/polypyrrole composite particles, add the stable gold particle of Trisodium Citrate then, utilize electrostatic interaction; The PS of gold particle/polypyrrole composite particles (the reference 3:Langmuir that obtained surface attachment; 2006,22,10163).Armes etc. have prepared PS/polypyrrole composite particles earlier, and the redox reaction original position of utilizing Au (III) ion and polypyrrole to take place then forms golden nanometer particle (reference 4:J.Mater.Chem., 2001,11,2363).Fujii has reported the building-up process of the pipe/polyhenylethylene nano latex particle that a kind of polypyrrole-palladium coats: adopting with the PVP K120 is that the polystyrene particle of stablizer is as substrate; The pyrrole monomer that adds can be enriched on the particle surface in the PVP K120 molecular layer, adds presoma PdCl2 then, makes it be attached to the polystyrene particle surface through redox reaction; Obtain composite particles (reference 5:Langmuir; 2010,26,6230).Selvan forms vesica with polystyrene-poly divinyl pyridine segmented copolymer in toluene solvant; Utilize the surface that hydrochloro-auric acid is enriched in vesica with the electrostatic interaction that gathers the divinyl pyridine then; The pyrroles and the hydrochloro-auric acid generation oxidation-reduction reaction that add subsequently, produced simultaneously golden nanometer particle and conductive polymers form composite structure (reference 6:Adv.Mater., 1998; 10,132).
The characteristics of the preparation process that above-mentioned report adopted do, one of which adopts the on-the-spot synthetic noble metal nano particles of redox reaction, and size of particles and monodispersity are difficult to effective control usually, and noble metal nano particles is positioned at the surface of composite particles; Secondly, in order to form composite structure effectively, all need matrix surface is designed or functionalization in advance, to improve the interaction between matrix and noble metal nano particles or its precursor.
Summary of the invention
The objective of the invention is to the preparation method that proposes a kind of polystyrene/polyaniline/noble metal nano particles composite particles and realize this composite structure.
The structure of polystyrene/polyaniline proposed by the invention/noble metal nano particles composite particles is: on the polystyrene particle surface, be covered with the shell of polyaniline, in the polyaniline shell and the surface, be embedded with noble metal nano particles.Among the present invention, noble metal nano particles is gold and silver or Pd nano particle; The weight ratio of noble metal nano particles and polystyrene particle is no more than 3.40; The weight ratio of polyaniline and PS is 1:2 ~ 1:20; The number average bead diameter of polystyrene particle is not less than 100 nanometers; The particle diameter ratio of polystyrene particle and noble metal nano particles is not less than 10.
Polystyrene/polyaniline with said structure/noble metal nano particles composite particles proposed by the invention; Its preparation method is: aniline monomer is added in the entry; Mix with pre-prepd polystyrene emulsion; Add pre-prepd monodispersed noble metal nano particles colloidal sol again; After mixing certain hour, add ammonium persulfate aqueous solution, slow dripping hydrochloric acid then, through reacting the Powdered polystyrene/polyaniline/noble metal nano particles composite particles that can obtain having the said structure characteristic behind the certain hour.Concrete preparation process is following:
1. the preparation of particle
The preparation of polystyrene emulsion can be adopted conventional polymerization methods such as dispersion polymerization, as, adopt the polymerization system that comprises monomer, pure medium or alcohol-water blending agent, non-ionic type amphiphilic macromolecular stablizer and oil-soluble initiator; Also can directly select commercially available polystyrene particle (microballoon) for use, water is mixed with polystyrene emulsion.
Monodispersed noble metal nano particles colloidal sol can adopt chemical reduction method, forms redox system by separately precursor and reductive agent, selects different reaction systems and reaction conditions to prepare the different various noble metal nano particles colloidal sols of particle diameter; Also can directly select commercially available monodispersed noble metal nano particles for use, water is mixed with noble metal nano particles colloidal sol.
2. the preparation of composite particles
Aniline is joined weight in its pure water of 100 ~ 1000 times, be cooled to 0 ° of C, stir down that ultra-sonic dispersion added polystyrene emulsion after 10 ~ 20 minutes, ultrasonic and stirred 10 ~ 20 minutes, 0 ° of C continues down to stir 1 ~ 3 hour subsequently.
In above-mentioned system, add noble metal nano particles colloidal sol, under 0 ° of C, stirred 0.5 ~ 1 hour.
The aqueous solution that in above-mentioned system, adds ammonium persulphate, dripping hydrochloric acid after dropwising, was reacted 4 hours under 0 ° of C then, rose to room temperature and continued reaction 20 hours.Behind the stopped reaction,, till upper solution becomes colorless,, obtain Powdered composite particles again through spinning, vacuum-drying with dilute hydrochloric acid solution centrifuge washing repeatedly.
Among the present invention, noble metal nano particles is gold and silver or Pd nano particle.
Among the present invention, the number average bead diameter of the polystyrene particle of selecting for use (microballoon) is not less than 100 nanometers, and the particle diameter ratio of polystyrene particle and noble metal nano particles is not less than 10.
Among the present invention, the weight ratio of noble metal nano particles and polystyrene particle is no more than 3.40.
Among the present invention, the solid content of polystyrene emulsion is 4 ~ 20wt%; The solid content of noble metal nano particles colloidal sol is 0.1 ~ 1.0wt%; The weight ratio of aniline and polystyrene particle is 1:2～1:20; The mol ratio of ammonium persulphate and aniline is about 1:1; The mol ratio of HCl and aniline is 1:1 ~ 1:2; The concentration range of hydrochloric acid is 0.25 ~ 1.00mol/L.
The characteristics of method proposed by the invention are: be matrix with the polystyrene particle 1., need not special surface design or functionalization, whole process of preparation is oversimplified; 2. noble metal nano particles can adopt prior art to prepare in advance, has enlarged its form, the isoparametric adjustable scope of size, thereby is easy to obtain the composite particles of different performance and characteristic.
Embodiment
Embodiment 1
In four-necked bottle, the 2.8g PVP K120 is dissolved in the 160ml Virahol, be warming up to 70 ° of C.Again the 0.2g Diisopropyl azodicarboxylate is dissolved in the 20g styrene monomer, under nitrogen protection, joins in the above-mentioned solution.Mechanical stirring, 24 hours postcooling of isothermal reaction are to room temperature.The gained emulsion is washed respectively 3 times with ethanol and deionized water through spinning successively, is scattered in to be made into the polystyrene particle emulsion that solid content is 4.2wt% in the pure water, and its number average bead diameter is 1800nm.
Under the room temperature; With 36ml concentration is that the aqueous solution of chloraurate of 0.122wt% joins in the 111ml deionized water, is warming up to the solution boiling under the magnetic agitation, adds the 1wt% citric acid three sodium solution of 3ml; Reacted 30 minutes, and obtained claret-colored golden nanometer particle colloidal sol and through the centrifugal 20ml of being concentrated to.Transmission electron microscope shows that it has monodispersity preferably, and particle diameter is about 30nm.
0.042g aniline is joined in the 10ml zero(ppm) water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring; Add 3g polystyrene particle emulsion, ultrasonic and stir about 15 minutes, close ultrasonic after; Add 7ml zero(ppm) water, continued to place ice-water bath 3 hours.Add the golden nanometer particle colloidal sol of 10ml and continue in the ice-water bath and stirred 1 hour, adding 0.84ml concentration is the ammonium persulfate aqueous solution of 1mol/L, stirs after 5 minutes, slowly drips the hydrochloric acid that 0.45ml concentration is 1mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with Hydrogen chloride centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal, after vacuum-drying obtains Powdered composite particles with supernatant liquid.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with golden nanometer particle.The particle diameter ratio of polystyrene particle and golden nanometer particle is 60.The weight ratio of golden nanometer particle and polystyrene particle is 0.09, and the weight ratio of polyaniline and PS is 1:3.75.
Embodiment 2
Adopt polystyrene emulsion and golden nanometer particle colloidal sol in the instance 1.
0.010g aniline is joined in the 10ml zero(ppm) water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring; Add 3g polystyrene particle emulsion, ultrasonic and stir about 15 minutes, close ultrasonic after; Add 7ml zero(ppm) water, continued to place ice-water bath 3 hours.Add the golden nanometer particle colloidal sol of 10ml and continue ice-water bath stirring 1 hour, adding 0.20ml concentration is the ammonium persulfate aqueous solution of 1mol/L, stirs after 5 minutes, slowly drips the hydrochloric acid that 0.11ml concentration is 1mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with Hydrogen chloride centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal again with supernatant liquid, after vacuum-drying obtains powdered samples.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with golden nanometer particle.The particle diameter ratio of polystyrene particle and golden nanometer particle is 60.The weight ratio of golden nanometer particle and polystyrene particle is 0.09, and the weight ratio of polyaniline and PS is 1:12.
Embodiment 3
Adopt the polystyrene emulsion in the instance 1.
Under the room temperature; With 36ml concentration is that the aqueous solution of chloraurate of 0.122wt% joins in the 111ml deionized water, is warming up to the solution boiling under the magnetic agitation, adds the 1wt% citric acid three sodium solution of 3ml; Reacted 30 minutes, and obtained claret-colored golden nanometer particle colloidal sol and through the centrifugal 10ml of being concentrated to.Transmission electron microscope shows that it has monodispersity preferably, and particle diameter is about 30nm.
0.042g aniline is joined in the 10ml zero(ppm) water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring; Add 3g polystyrene particle emulsion, ultrasonic and stir about 15 minutes, close ultrasonic after; Add 7ml zero(ppm) water, continued to place ice-water bath 3 hours.Add the golden nanometer particle colloidal sol of 10ml and continue in the ice-water bath and stirred 1 hour, adding 0.84ml concentration is the ammonium persulfate aqueous solution of 1mol/L, stirs after 5 minutes, slowly drips the hydrochloric acid that 0.45ml concentration is 1mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with Hydrogen chloride centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal, after vacuum-drying obtains Powdered composite particles with supernatant liquid.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with golden nanometer particle.The particle diameter ratio of polystyrene particle and golden nanometer particle is 60.The weight ratio of golden nanometer particle and polystyrene particle is 0.15, and the weight ratio of polyaniline and PS is 1:3.75.
Embodiment 4
Adopt the polystyrene emulsion in the instance 1.
Under the room temperature; With 36ml concentration is that the aqueous solution of chloraurate of 0.122wt% joins in the 113ml deionized water; Be warming up to the solution boiling under the magnetic agitation; Add the 1wt% citric acid three sodium solution of 0.84ml, reacted 30 minutes, obtain claret-colored golden nanometer particle colloidal sol and through the centrifugal 20ml of being concentrated to.Transmission electron microscope shows that it has monodispersity preferably, and particle diameter is about 80nm.
0.014g aniline is joined in the 10ml zero(ppm) water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring; Add 3g polystyrene particle emulsion, ultrasonic and stir about 15 minutes, close ultrasonic after; Add 7ml zero(ppm) water, continued to place ice-water bath 3 hours.Add the golden nanometer particle colloidal sol of 10ml and continue ice-water bath stirring 1 hour, adding 0.28ml concentration is the ammonium persulfate aqueous solution of 1mol/L, stirs after 5 minutes, slowly drips the hydrochloric acid that 0.15ml concentration is 1mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with Hydrogen chloride centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal, after vacuum-drying obtains Powdered composite particles with supernatant liquid.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with golden nanometer particle.The particle diameter ratio of polystyrene particle and golden nanometer particle is 23.The weight ratio of golden nanometer particle and polystyrene particle is 0.08, and the weight ratio of polyaniline and PS is 1:9.5.
Embodiment 5
Adopt the polystyrene emulsion in the instance 1.
Under the room temperature; With 15ml concentration is that the silver nitrate aqueous solution of 0.216wt% joins in the 180ml deionized water; Be warming up to the solution boiling under the magnetic agitation, add the 10wt% citric acid three sodium solution of 0.54ml, reacted 30 minutes; Obtain yellowish green Nano silver grain colloidal sol and through the centrifugal 10ml of being concentrated to, transmission electron microscope shows that its particle diameter is about 60nm.
0.042g aniline is joined in the 10ml zero(ppm) water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring; Add 3g polystyrene particle emulsion, ultrasonic and stir about 15 minutes, close ultrasonic after; Add 7ml zero(ppm) water, continued ice-water bath 3 hours.Add the Nano silver grain colloidal sol of 10ml and continue ice-water bath stirring 1 hour, adding 0.84ml concentration is the ammonium persulfate aqueous solution of 1mol/L, stirs after 5 minutes, slowly drips the hydrochloric acid that 0.45ml concentration is 1mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with Hydrogen chloride centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal, after vacuum-drying obtains Powdered composite particles with supernatant liquid.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with Nano silver grain.The particle diameter ratio of polystyrene particle and Nano silver grain is 30.The weight ratio of Nano silver grain and polystyrene particle is 0.10, and the weight ratio of polyaniline and PS is 1:3.75.
Embodiment 6
Adopt the polystyrene emulsion in the instance 1.
Adopt the Nano silver grain colloidal sol in the instance 5.
0.010g aniline is joined in the 10ml zero(ppm) water, and ice-water bath is cooled to 0 ° of C, and ultra-sonic dispersion is after about 15 minutes under mechanical stirring; Add 3g polystyrene particle emulsion, ultrasonic and stir about 15 minutes, close ultrasonic after; Add 7ml zero(ppm) water, continued ice-water bath 3 hours.Add the Nano silver grain colloidal sol of 10ml and continue ice-water bath stirring 1 hour, adding 0.20ml concentration is the ammonium persulfate aqueous solution of 1mol/L, stirs after 5 minutes, slowly drips the hydrochloric acid that 0.11ml concentration is 1mol/L.Reaction is 4 hours in ice-water bath, rises to room temperature and continues reaction 20 hours.Stopped reaction with Hydrogen chloride centrifuge washing repeatedly, till upper solution becomes colorless, separates throw out through centrifugal, after vacuum-drying obtains Powdered composite particles with supernatant liquid.The structure of this composite particles is: on the polystyrene microsphere surface, be covered with a polyaniline shell, in the polyaniline shell and the surface, be embedded with Nano silver grain.The particle diameter ratio of polystyrene particle and Nano silver grain is 30.The weight ratio of Nano silver grain and polystyrene particle is 0.10, and the weight ratio of polyaniline and PS is 1:12.
Claims (7)
1. polystyrene/polyaniline/noble metal nano particles composite particles is characterized in that being covered with on the polystyrene particle surface shell of polyaniline, in the polyaniline shell and the surface, is embedded with noble metal nano particles; The weight ratio of noble metal nano particles and polystyrene particle is no more than 3.40; The weight ratio of polyaniline and PS is 1: 2 ~ 1: 20; The number average bead diameter of polystyrene particle is not less than 100 nanometers; The particle diameter ratio of polystyrene particle and noble metal nano particles is not less than 10.
2. according to the described polystyrene/polyaniline of claim 1/noble metal nano particles composite particles, it is characterized in that noble metal nano particles is gold and silver or Pd nano particle.
3. the preparation method of polystyrene/polyaniline/noble metal nano particles composite particles is characterized in that the preparation process is following:
A. the preparation of particle
Select polystyrene particle for use, water is mixed with the polystyrene emulsion that solid content is 4 ~ 20 wt%;
Select monodispersed noble metal nano particles for use, water is mixed with the noble metal nano particles colloidal sol that solid content is 0.1 ~ 1.0 wt%; Noble metal nano particles is gold and silver or Pd nano particle;
B. the preparation of composite particles
Aniline is joined weight in its pure water of 100 ~ 1000 times, be cooled to 0 ° of C, stir down that ultra-sonic dispersion added polystyrene emulsion after 10 ~ 20 minutes, ultrasonic and stirred 10 ~ 20 minutes, 0 ° of C continues down to stir 1 ~ 3 hour subsequently;
In above-mentioned system, add noble metal nano particles colloidal sol, under 0 ° of C, stirred 0.5 ~ 1 hour;
The aqueous solution that in above-mentioned system, adds ammonium persulphate, dripping hydrochloric acid then is after dripping off; 0 ° of C reacted 4 hours down; Rise to room temperature and continue reaction 20 hours, with dilute hydrochloric acid solution centrifuge washing repeatedly, till upper solution becomes colorless; Through spinning, vacuum-drying, obtain Powdered composite particles again.
4. according to the preparation method of the described polystyrene/polyaniline of claim 3/noble metal nano particles composite particles, the weight ratio that it is characterized in that aniline and polystyrene particle is 1: 2 ~ 1: 20.
5. according to the preparation method of the described polystyrene/polyaniline of claim 3/noble metal nano particles composite particles, the mol ratio that it is characterized in that ammonium persulphate and aniline is 1:1.
6. according to the preparation method of the described polystyrene/polyaniline of claim 3/noble metal nano particles composite particles, the mol ratio that it is characterized in that HCl and aniline is 1:1 ~ 1:2, and the concentration of hydrochloric acid scope is 0.25 ~ 1.00 mol/L.
7. according to the preparation method of the described polystyrene/polyaniline of claim 3/noble metal nano particles composite particles, it is characterized in that the particle diameter ratio of polystyrene particle particle diameter and noble metal nano particles is not less than 10; The number average bead diameter of polystyrene particle is not less than 100 nanometers; The weight ratio of noble metal nano particles and polystyrene particle is no more than 3.40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110080358A CN102206356B (en) | 2011-03-31 | 2011-03-31 | Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110080358A CN102206356B (en) | 2011-03-31 | 2011-03-31 | Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102206356A CN102206356A (en) | 2011-10-05 |
| CN102206356B true CN102206356B (en) | 2012-10-24 |
Family
ID=44695440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110080358A Expired - Fee Related CN102206356B (en) | 2011-03-31 | 2011-03-31 | Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102206356B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702636A (en) * | 2012-06-14 | 2012-10-03 | 南京大学 | Polystyrene/polyaniline/magnetic nanoparticle composite particle and preparation method thereof |
| CN104974519B (en) * | 2015-08-03 | 2017-10-24 | 安徽理工大学 | A kind of preparation method of fibrous Pd/PANI nano composite materials |
| CN105061759B (en) * | 2015-08-03 | 2017-10-24 | 安徽理工大学 | A kind of preparation method of Pd/PANI nano composite materials |
| CN105315565B (en) * | 2015-11-27 | 2018-08-03 | 湖北大学 | A kind of sulfonated polystyrene/polyaniline/nano silver complex microsphere and preparation method thereof |
| CN106409381B (en) * | 2016-11-02 | 2018-02-16 | 宁波鸿源电子科技有限公司 | A kind of polyaniline strengthens conductive aluminium flake |
| CN109921048B (en) * | 2019-03-18 | 2020-12-15 | 岭南师范学院 | Pd/Ag/PANI nano composite material and low-temperature preparation method and application thereof |
| CN110459342A (en) * | 2019-08-16 | 2019-11-15 | 戴洪卫 | It is a kind of with the composite high-molecular conductive material and preparation method thereof for stablizing conductivity |
| CN110791090A (en) * | 2019-10-11 | 2020-02-14 | 杭州师范大学 | Macroscopic large-area two-dimensional dual-response high-plasma-sensitivity switch polyaniline @ gold nanoparticle core-shell-structure single-layer film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958658A (en) * | 2006-11-21 | 2007-05-09 | 南京大学 | Method for preparing conductive, high molecular compound particles of polystyrene / polyaniline |
| CN101225204A (en) * | 2007-12-25 | 2008-07-23 | 北京科技大学 | Method for preparing morphology-controlled polyphenylethene/polyaniline conductive polymeric composite microspheres |
| CN101863453A (en) * | 2010-06-13 | 2010-10-20 | 南京大学 | Preparation method of polystyrene/Au compound particle |
-
2011
- 2011-03-31 CN CN201110080358A patent/CN102206356B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958658A (en) * | 2006-11-21 | 2007-05-09 | 南京大学 | Method for preparing conductive, high molecular compound particles of polystyrene / polyaniline |
| CN101225204A (en) * | 2007-12-25 | 2008-07-23 | 北京科技大学 | Method for preparing morphology-controlled polyphenylethene/polyaniline conductive polymeric composite microspheres |
| CN101863453A (en) * | 2010-06-13 | 2010-10-20 | 南京大学 | Preparation method of polystyrene/Au compound particle |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102206356A (en) | 2011-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102206356B (en) | Polystyrene/ (precious metal nanoparticles @ polyaniline) composite particles and preparation method thereof | |
| Sakai et al. | Mechanism of gold metal ion reduction, nanoparticle growth and size control in aqueous amphiphilic block copolymer solutions at ambient conditions | |
| Ku et al. | Particles with tunable porosity and morphology by controlling interfacial instability in block copolymer emulsions | |
| Naka et al. | Temperature-dependent reversible self-assembly of gold nanoparticles into spherical aggregates by molecular recognition between pyrenyl and dinitrophenyl units | |
| Selvan et al. | Block copolymer mediated synthesis of gold quantum dots and novel gold− polypyrrole nanocomposites | |
| Kuijk et al. | Synthesis of monodisperse, rodlike silica colloids with tunable aspect ratio | |
| Bleach et al. | In situ formation of polymer–gold composite nanoparticles with tunable morphologies | |
| Dhar et al. | Self-assembly and catalytic activity of metal nanoparticles immobilized in polymer membrane prepared via layer-by-layer approach | |
| Tang et al. | Poly (N-vinyl-2-pyrrolidone)(PVP)-capped dendritic gold nanoparticles by a one-step hydrothermal route and their high SERS effect | |
| Zhang et al. | Facile incorporation of aggregation-induced emission materials into mesoporous silica nanoparticles for intracellular imaging and cancer therapy | |
| Bai et al. | Synthesis of narrow or monodisperse poly (divinylbenzene) microspheres by distillation− precipitation polymerization | |
| Deng et al. | Polymeric janus particles with hierarchical structures | |
| Chen et al. | Hollow/rattle-type mesoporous nanostructures by a structural difference-based selective etching strategy | |
| Tian et al. | Simple strategy for preparation of core colloids modified with metal nanoparticles | |
| Kim et al. | Gold-decorated block copolymer microspheres with controlled surface nanostructures | |
| Yang et al. | Facile synthesis of high-concentration, stable aqueous dispersions of uniform silver nanoparticles using aniline as a reductant | |
| Cao et al. | In situ synthesis of catalytic active Au nanoparticles onto gibbsite–polydopamine core–shell nanoplates | |
| Yang et al. | One-pot synthesis of monodisperse noble metal@ resorcinol-formaldehyde (M@ RF) and M@ Carbon core–shell nanostructure and their catalytic applications | |
| Bourret et al. | 1D Cu (OH) 2 nanomaterial synthesis templated in water microdroplets | |
| JP4094277B2 (en) | Preparation of metal nanoparticles using shell-crosslinked micelles as templates | |
| Dorris et al. | Preparation and characterization of polyelectrolyte-coated gold nanoparticles | |
| Mangeney et al. | Latex and hollow particles of reactive polypyrrole: preparation, properties, and decoration by gold nanospheres | |
| Liu et al. | Multilayer magnetic composite particles with functional polymer brushes as stabilizers for gold nanocolloids and their recyclable catalysis | |
| Kim et al. | Room-temperature synthesis of hollow polymer microparticles with an open hole on the surface and their application | |
| Wang et al. | Homo-and co-polymerization of polysytrene-block-poly (acrylic acid)-coated metal nanoparticles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121024 Termination date: 20130331 |