CN101020783A - Nanometer composition particle of poly-o-phenyldiamine and silver and its prepn process - Google Patents
Nanometer composition particle of poly-o-phenyldiamine and silver and its prepn process Download PDFInfo
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- CN101020783A CN101020783A CN 200710037534 CN200710037534A CN101020783A CN 101020783 A CN101020783 A CN 101020783A CN 200710037534 CN200710037534 CN 200710037534 CN 200710037534 A CN200710037534 A CN 200710037534A CN 101020783 A CN101020783 A CN 101020783A
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Abstract
The present invention discloses one kind of semiconductive nanometer composition particle of poly-o-phenyldiamine and metal silver. The nanometer composition particle of poly-o-phenyldiamine and metal silver is prepared through the first chemical oxidation process to prepare poly-o-phenyldiamine, the subsequent adding poly-o-phenyldiamine into silver ion solution to react, and final filtering and drying. The preparation process of the present invention is simple, feasible, low in silver consumption, low in cost, and suitable for industrial production. The present invention provides new way of preparing nanometer composition particle of poly-o-phenyldiamine and metal silver.
Description
Technical field
The invention belongs to the nano-complex particle preparation method technical field of semiconduction poly-o-phenylenediamine and metal.
Background technology
The matrix material of electroactive polymer and metal has obtained extensive studies and application with the physics and the chemical property of excellence.As a kind of important aromatic diamines base polymer, poly-o-phenylenediamine can provide more active free amino group and imido grpup, and the mixture of it and metal shows excellent performance in fields such as electrocatalysis, electrode modification, transmitters.With the matrix material that the metal platinum particles high dispersing is made in the poly-o-phenylenediamine film, have well electroactive and to H
2O
2Electrical catalyze reduction, can be used for making biosensor (Cai L T, Chen H Y.Electrocatalytic reduction of hydrogen peroxide at platinummicroparticles dispersed in a poly (o-phenylenediamine) film.Sensors and Actuators B, 1999,55:14-18).The modified electrode that the mixture introducing poly-o-phenylenediamine film of metal platinum and nail or tin is made can be directly used in the electrocatalysis field, and oxidization of methanol reaction had electrocatalysis characteristic (Golikand A N preferably, Golabi S M, Maragheh M G, et al.Electrocatalytic oxidation of methanol on (Pb) lead modified by Pt, Pt-Ru and Pt-Sn microparticlesdispersed into poly (o-phenylenediamine) film.Journal of Power Sources, 2005,145:116-123).The modified electrode of poly-o-phenylenediamine and metal platinum can reach three times of platinum electrode to the oxidization of methanol current peak.Why polyphenyl diamines and metallics mixture have excellent electrocatalysis characteristic is because the polyphenyl diamines has good dissemination as body material to metallics, the specific surface area of metal is bigger, thereby micromolecular electrocatalysis characteristic is better than the pure metal electrode.
The preparation of poly-o-phenylenediamine and metal composite adopts electrochemical method, at first prepares the poly-o-phenylenediamine film at electrode surface, makes mixture by the in-situ reducing metal ion or with the self-assembly layer by layer of metallic particles then.Researchs such as Golabi at first obtain the poly-o-phenylenediamine film in the electrode surface polymerization by electrochemical oxidation, then electrode is placed chloroplatinic solution, go out metal platinum particles by electrochemical reduction, be deposited in the polymeric film, thereby made mixture (Golabi S M, Nozad A.Electrocatalytic oxidation of methanol on electrodes modified by platinum microparticles dispersedinto poly (o-phenylenediamine) film.Journal of Electroanalytical Chemistry, 2002,521:161-167).Yuan etc. are at electrode surface electrochemically oxidative polymerization thing one deck poly-o-phenylenediamine film, to in 4 ℃ gold size solution, flood an evening through the electrode after washing and the drying then, thereby repeat these two steps and obtained double-deck self-assembly poly-o-phenylenediamine/nanometer gold composite membrane (Yuan R, Zhang L Y, Li Q F, et al.A label-free amperometric immunosenor based onmulti-layer assembly of polymerized o-phenylenediamine and gold nanoparticles for determinationof Japanese B encephalitis vaccine.Analytica Chimica Acta, 2005,531:1-5).
These methods at first generate polymeric film all based on electrochemical polymerization on electrode surface, because reacting environment is near electrode surface, the output of mixture is subjected to the electrode area size-dependence, can't obtain a large amount of organic-inorganic nano composite particless.Therefore, the poly-o-phenylenediamine that a kind of new easy, economy of exploitation, productive rate height, suitability are strong and the nanometer particle process method of metal are very important.In addition, at home and abroad in the preparation research about poly-o-phenylenediamine/metal composite, used metal mostly is gold and platinum, does not also see about the report of poly-o-phenylenediamine with the preparation method of the nano-complex particle of silver.
Summary of the invention
Purpose of the present invention just provides the preparation method of the nano-complex particle of a kind of simple, cost-effective poly-o-phenylenediamine and silver formation.
Another object of the present invention provides with the poly-o-phenylenediamine of method for preparing and the nano-complex particle of silver formation.
The concrete technical scheme that the present invention takes is as follows:
The preparation method of poly-o-phenylenediamine and silver-colored nano-complex particle, this method prepare poly-o-phenylenediamine by chemical oxidization method, and poly-o-phenylenediamine is added in the silver ion solution react then, at last with reacting liquid filtering, dry getting final product.
The preparation method of above-mentioned poly-o-phenylenediamine and silver-colored nano-complex particle, the concrete steps that wherein said chemical oxidization method prepares poly-o-phenylenediamine are: add O-Phenylene Diamine monomer and oxygenant in the acid reaction medium respectively, after waiting to dissolve oxidizing agent solution added the O-Phenylene Diamine monomer solution, it is reacted completely, and aftertreatment can obtain the poly-o-phenylenediamine powder.
Said oxygenant can be ammonium persulphate, Sodium Persulfate, potassium bichromate, Potassium Persulphate (K
2S
2O
8) or iron trichloride (FeCl
3).Oxygenant and monomeric mol ratio be preferably 1: 1～and 3: 1.Because polymeric reaction temperature has considerable influence to polymerization rate, low excessively temperature of reaction is unfavorable to the polyreaction of mphenylenediamine, and therefore in the present invention, polymeric reaction temperature is preferably 70～118 ℃.The present invention adopts currently known methods polymerisate to be separated aftertreatments such as purification, and this aftertreatment comprises removes the monomer of not participating in reaction that remains in the reaction mixture, the oligopolymer that reaction generates, and residual oxygenant.Treatment step is: filtration, deionized water wash, precipitation and drying.
The reaction times of poly-o-phenylenediamine particle of the present invention and silver ion solution generally was controlled at 0.5～24 hour.Said silver ion solution is silver nitrate solution preferably.
Poly-o-phenylenediamine that the present invention is prepared and Nano silver grain are through the laser particle analyzer analysis, and median size is 70nm～170nm, and by TEM photo (Fig. 2) as can be known, the particle diameter of silver particles is about 20nm in the nano-complex.By its electron diffraction pattern (Fig. 3), silver is the monocrystalline form as can be known.
The present invention directly contacts poly-o-phenylenediamine with silver ion solution, is silver-colored simple substance by the amino in the polymkeric substance with silver ion reduction, and the reductive nanometer silver is deposited on and forms poly-o-phenylenediamine and silver-colored nanoparticle in the polymer particle.This mixture is expected to be used for fields such as electrocatalysis, electrode modification, transmitter.
Beneficial effect of the present invention: it is simple that method of the present invention prepares the operating process of organic-inorganic nano composite particles, reacts spontaneous carrying out, and silver consumes less, with low cost, and the composite particles production scale that makes is bigger.The present invention provides cost-effective new way for the preparation of poly-o-phenylenediamine and silver-colored nano-complex, and the functional study for poly-o-phenylenediamine and silver-colored nano-complex provides abundant basic substance simultaneously.
Description of drawings
Fig. 1 is the laser particle size figure of poly-o-phenylenediamine/silver-colored nano-complex particle.
Fig. 2 is the TEM photo of poly-o-phenylenediamine/silver-colored nano-complex particle.
Fig. 3 is the electron diffraction pattern of silver-colored monocrystalline in poly-o-phenylenediamine/silver-colored nano-complex particle.
Fig. 4 is the XPS of poly-o-phenylenediamine and 0.5 hour gained nano-complex particle of Silver Nitrate reaction.
Fig. 5 is the XPS of poly-o-phenylenediamine and 24 hours gained nano-complex particles of Silver Nitrate reaction.
Embodiment
Embodiment 1:
Accurately take by weighing 6.48g (0.06mol) O-Phenylene Diamine monomer and add in the Glacial acetic acid, place 40 ℃ water-bath, stir and impel its dissolving.Took by weighing 13.68g (0.06mol) ammonium persulphate than 1: 1 by the oxygenant monomer, be transferred in the 100mL beaker and add and make it abundant dissolving in the 6mL deionized water.Oxidizing agent solution is added in the monomeric glacial acetic acid solution of O-Phenylene Diamine, continued back flow reaction 72 hours.Reaction finishes, filtration drying obtain the mixing black powder shape poly-o-phenylenediamine of attitude.
Output by the prepared O-Phenylene Diamine polymkeric substance of present embodiment is 2.59g, and productive rate is 40.0%.The specific conductivity of the polymer powder that records with pressed disc method is 1.8 * 10
-10S/cm.
Embodiment 2:
Accurately take by weighing 6.48g (0.06mol) O-Phenylene Diamine monomer and add in the Glacial acetic acid, place 40 ℃ water-bath, stir and impel its dissolving.Took by weighing 27.36g (0.12mol) ammonium persulphate than 2: 1 by the oxygenant monomer, be transferred in the 100ml beaker and add and make it abundant dissolving in the 6ml deionized water.Oxidizing agent solution is added in the monomeric glacial acetic acid solution of O-Phenylene Diamine, continued back flow reaction 72 hours.Reaction finishes, filtration drying obtain the mixing black powder shape poly-o-phenylenediamine of attitude.
Output by the prepared O-Phenylene Diamine polymkeric substance of present embodiment is 5.15g, and productive rate is 79.4%.The specific conductivity of the polymer powder that records with pressed disc method is 3.0 * 10
-10S/cm.
Embodiment 3:
Accurately take by weighing 6.48g (0.06mol) O-Phenylene Diamine monomer and add in the Glacial acetic acid, place 40 ℃ water-bath, stir and impel its dissolving.Took by weighing 41.04g (0.18mol) ammonium persulphate than 3: 1 by the oxygenant monomer, be transferred in the 100ml beaker and add and make it abundant dissolving in the 6ml deionized water.Oxidizing agent solution is added in the monomeric glacial acetic acid solution of O-Phenylene Diamine, continued back flow reaction 72 hours.Reaction finishes, filtration drying obtain the mixing black powder shape poly-o-phenylenediamine of attitude.
Output by the prepared O-Phenylene Diamine polymkeric substance of present embodiment is 4.61g, and productive rate is 71.2%, and specific conductivity is less than 1 * 10
-12S/cm.
Embodiment 3～6
Getting oxygen digital ratio is synthetic doping attitude poly-o-phenylenediamine 50mg under 1/1 condition, and placing the 25mL starting point concentration is the silver nitrate solution of 0.50mmol/L, and the lucifuge stirring reaction is 24 hours in 30 ℃ of waters bath with thermostatic control.Reaction finishes, and filtration drying obtains poly-o-phenylenediamine/nanometer silver composite particles, detects through laser particle analyzer, and its number average bead diameter is 169nm, and wherein Yin content is 6.2wt%;
Under the similarity condition, initial concentration of silver ions is 2.5mmol/L, detects through laser particle analyzer, and poly-o-phenylenediamine/silver-colored nano-complex particle number average bead diameter is 92nm, and silver content is 9.8wt%.
Under the similarity condition, initial concentration of silver ions is 5.0mmol/L, detects through laser particle analyzer, and poly-o-phenylenediamine/silver-colored nano-complex particle number average bead diameter is 83.4nm, and silver content is 14.5wt%.
Under the similarity condition, initial concentration of silver ions is 10.77mmol/L, detects (Fig. 1) through laser particle analyzer, and poly-o-phenylenediamine/silver-colored nano-complex particle number average bead diameter is 77nm, and silver content is 21.6wt%.Wherein the nanometer silver about 20nm is dispersed in the poly-o-phenylenediamine matrix, sees Fig. 2 TEM photo, and nanometer silver exists with the monocrystalline form, and its electron diffraction pattern is seen Fig. 3.
Under the similarity condition, initial concentration of silver ions is 21.55mmol/L, detects through laser particle analyzer, and poly-o-phenylenediamine/silver-colored nano-complex particle number average bead diameter is 100nm, and silver content is 25.5wt%.
Embodiment 7～8
Getting oxygen digital ratio is synthetic doping attitude poly-o-phenylenediamine 50mg under 1/1 condition, and placing 25mL concentration is the silver nitrate solution of 43.09mmol/L, and the lucifuge stirring reaction is 0.5 hour in 30 ℃ of waters bath with thermostatic control.Reaction finishes, filtration drying obtains poly-o-phenylenediamine and silver-colored composite particles, through residual concentration of silver ions titrimetry, push away poly-o-phenylenediamine with silver composite particles in silver content be 24.0wt%, through XPS (Fig. 4) surface-element content analysis, push away in the composite particles of poly-o-phenylenediamine and silver silver content be 19.7wt%, and silver wherein is with the coexistence of simple substance attitude and ionic state, the two weight ratio is 44/56; Under the similarity condition, the reaction times is extended for 24 hours, and the silver content titrimetry is 29.3wt% in the composite particles of poly-o-phenylenediamine and silver; XPS (Fig. 5) analyzes and to be 20.3wt%, and silver wherein is with simple substance attitude and ionic state coexistence, and the two weight ratio is 61/39.
By above embodiment as seen, use oxidation reduction process to prepare poly-o-phenylenediamine and silver-colored nano-complex particle, operation is simple, only need in certain density silver nitrate solution, to add a certain amount of poly-o-phenylenediamine, and stirring reaction for some time get final product, and this reaction is spontaneously to carry out economical and effective, need not increase equipment and additional reducing agent expense, can obtain a large amount of mixtures.Wherein silver content can artificially be controlled, and adjusts as required.This method can obtain homodisperse nanometer silver monocrystalline in the poly-o-phenylenediamine matrix.
Claims (9)
1, the preparation method of poly-o-phenylenediamine and silver-colored nano-complex particle, this method prepare poly-o-phenylenediamine by chemical oxidization method, and poly-o-phenylenediamine is joined in the silver ion solution react then, at last with reacting liquid filtering, dry getting final product.
2, the preparation method of poly-o-phenylenediamine as claimed in claim 1 and silver-colored nano-complex particle, it is characterized in that: the concrete steps that said chemical oxidization method prepares poly-o-phenylenediamine are: add O-Phenylene Diamine monomer and oxygenant in the acid reaction medium respectively, after waiting to dissolve oxidizing agent solution added the O-Phenylene Diamine monomer solution, it is reacted completely, and aftertreatment gets final product.
3, the preparation method of poly-o-phenylenediamine as claimed in claim 2 and silver-colored nano-complex particle is characterized in that: said oxygenant is ammonium persulphate, Sodium Persulfate, potassium bichromate, Potassium Persulphate or iron trichloride.
4, the preparation method of poly-o-phenylenediamine as claimed in claim 2 and silver-colored nano-complex particle is characterized in that: oxygenant and monomeric mol ratio are 1: 1～3: 1.
5, the preparation method of poly-o-phenylenediamine as claimed in claim 2 and silver-colored nano-complex particle is characterized in that: polymeric reaction temperature is 70～118 ℃.
6, the preparation method of poly-o-phenylenediamine as claimed in claim 1 and silver-colored nano-complex particle is characterized in that: the reaction times of poly-o-phenylenediamine particle and silver ion solution is 0.5～24 hour.
7, the preparation method of poly-o-phenylenediamine as claimed in claim 1 and silver-colored nano-complex particle is characterized in that: said silver ion solution is a silver nitrate solution.
8, the prepared poly-o-phenylenediamine of preparation method and the silver composite nano particles of arbitrary described poly-o-phenylenediamine of claim 1～7 and silver-colored nano-complex particle.
9, poly-o-phenylenediamine as claimed in claim 8 and silver composite nano particles is characterized in that: the median size of composite particles is 70nm～170nm.
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| JPS5239638B2 (en) * | 1973-09-17 | 1977-10-06 | ||
| CN1185545C (en) * | 2000-09-26 | 2005-01-19 | 富士胶片株式会社 | Silver halide picture photosensitive material, compound forming azoheterocyclic dye, and process for preparing dye |
| US7101961B2 (en) * | 2004-06-15 | 2006-09-05 | Changchun Institute Of Applied Chemistry Chinese Academy Of Sciences | Method for preparation of poly(o-phenylenediamine) Nano-belt |
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Granted publication date: 20081119 Termination date: 20110213 |