CN1159125C - Process for preparing metallic nanoparticles with redox activity - Google Patents
Process for preparing metallic nanoparticles with redox activity Download PDFInfo
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- CN1159125C CN1159125C CNB021179522A CN02117952A CN1159125C CN 1159125 C CN1159125 C CN 1159125C CN B021179522 A CNB021179522 A CN B021179522A CN 02117952 A CN02117952 A CN 02117952A CN 1159125 C CN1159125 C CN 1159125C
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Abstract
The present invention belongs to a preparation method for metal nanometer particles with redox activity. Chloroauric acid, chloroplatinic acid, silver nitrate or palladium chloride are used as predecessors. 4-octyl amine bromide and 4-octyl ammonia chloride are used as phase transfer catalysts. Ferrocene with redox activity, quinoline, and a thiol derivant of anthraquinone are used as stabilizers. Sodium borohydride and trisodium citrate dihydrate are used as reduction agents. Metal nanometer particles with redox activity, of which the diameters are between 1.7 nm and 3.3 nm are obtained through a phase transfer reduction method. The metal nanometer particles can be used as labels applied to biologic immune sensors. Compared with the traditional enzymic labelling method, radioactive labelling method and fluorescent labelling method, the electrochemical detection can raise the sensitivity by 2 to 3 orders of magnitude.
Description
Technical field: the preparation method who the invention belongs to metal nanoparticle with redox active.
Background technology: metal nanoparticle is with a wide range of applications at numerous areas such as molecular device, chemical/biological sensors, catalysis, photoelectron materials.The preparation of metal nanoparticle generally based on sol-gel process, promptly utilizes reducing agent reducing metal salt, and sintering obtains nano particle then.The particle diameter of the nano particle that this method obtains is bigger, 〉=30nm, and particle size distribution range is wide, and is difficult to solve agglomeration traits.
At J.Chem.Soc., Chem.Commun., 1994,801-802, people such as Brust disclose a kind of new method of synthetic gold nano grain.Promptly in sodium borohydride reduction agent reduction gold chloride, add the lauryl mercaptan stabilizing agent, finally obtain the golden nanometer particle that surface-assembled has the lauryl mercaptan stabilizing agent.The gold nano grain particle diameter that this method obtains is little ,≤5nm, and particle size distribution range is narrow, and≤2nm be difficult for to reunite, and can separate out and be dissolved in non-polar organic solvent repeatedly, can stable existence more than half a year even be exposed in the air also with powder type.This method not only can be used for preparing the nano particle of gold, can also be used to preparation silver, platinum, the nano particle of a series of noble metals such as palladium.Yet because lauryl mercaptan do not have redox active, the metal nanoparticle that obtains is also for non-oxide reducing activity, and this will limit the further application of metal nanoparticle.
Summary of the invention: the purpose of this invention is to provide a kind of preparation method with metal nanoparticle of redox active.
With gold chloride, chloroplatinic acid, silver nitrate, palladium bichloride is a predecessor, and with four octyl group amine bromides, four octyl group ammonium chlorides are phase transfer catalyst, to have the ferrocene of redox active, quinoline, the thiol derivative of anthraquinone is a stabilizing agent, with sodium borohydride, natrium citricum is a reducing agent, through the phase transfer reducing process, obtain diameter between 1.7nm～3.3nm, have the metal nanoparticle of redox active.This metal nanoparticle can be used as label and is applied in the biological immune sensing device.With traditional enzyme labeling, radio-labeled, fluorescent marker method is compared, and Electrochemical Detection can improve sensitivity 2-3 the order of magnitude.
Synthesis step is as follows:
With the predecessor gold chloride, chloroplatinic acid, silver nitrate, palladium bichloride is soluble in water, wiring solution-forming, concentration≤0.01mol/l; With the stabilizing agent ferrocene, the thiol derivative of quinoline or anthraquinone is dissolved in the toluene, is made into stabiliser solution, and wherein the mol ratio of predecessor and stabilizing agent is 1: 1～4; With phase transfer catalyst four octyl group amine bromides, four octyl group ammonium chlorides are dissolved in the toluene, are made into the phase transfer catalysis (PTC) agent solution, and the mol ratio that makes predecessor and phase transfer catalyst is 1: 1～2; Borane reducing agent sodium hydride or natrium citricum is soluble in water, be made into reductant solution, the mol ratio that makes predecessor and reducing agent is 1: 10～15, under the room temperature, the phase transfer catalysis (PTC) agent solution is added in the predecessor that stirs, and under the effect of phase transfer catalyst, predecessor is transferred in the toluene organic facies; The toluene organic facies is separated, stabilizing agent is added above-mentioned organic facies slowly, stir; Then reducing agent is added organic facies rapidly, continue to stir; The organic facies that obtains in the mixed solution is separated, remove toluene solvant 30 ℃～50 ℃ following decompression distillation, obtain the product of black, utilize a large amount of water, ethanol, the above-mentioned product of washing that acetone is continuous is removed excessive thiol stabilizer and phase transfer catalyst, obtain diameter between 1.7nm～3.3nm, have the metal nanoparticle of redox active.
The specific embodiment
Embodiment 1
The mol ratio of gold chloride and 4-ferrocene benzenethiol is 1, the mol ratio of gold chloride and four octyl group amine bromides is 1: 2, the mol ratio of gold chloride and sodium borohydride is 1: 10, under the room temperature, four octyl group bromination amine aqueous solutions are under agitation added chlorauric acid solution, continue to stir, find that water gradually becomes colourless and upper organic phase changes into orange-yellowly, shows that gold chloride transfers in the organic facies.Organic facies is separated.4-ferrocene benzenethiol is added above-mentioned organic facies, stir, solution gradually becomes white.Then sodium borohydride solution is added in the solution of white, find that this solution becomes black very soon, show to have generated gold nano grain.Continue to stir, the organic facies in the solution that obtains is separated.Remove toluene solvant 30 ℃ of following decompression distillation, obtain black solid.Utilize a large amount of water, ethanol, the above-mentioned black solid of washing that acetone is continuous is removed excessive thiol stabilizer and phase transfer catalyst, obtains pure product.Transmission electron microscope confirms that the average grain diameter of this nano particle is 2.5nm, and distribution is less than 2nm.Its oxidation-reduction potential of cyclic voltammetry experiment proof is 0.5V, with respect to the Ag/AgCl reference electrode, down together.This metal nanoparticle has been used for the mediator of biological immune sensing device.
Embodiment 2
The mol ratio of silver nitrate and 4-ferrocene benzenethiol is 1: 2, and the mol ratio of silver nitrate and four octyl group ammonium chlorides is 1: 1, and vacuum distillation temperature is 40 ℃, and other condition is identical with embodiment 1.Transmission electron microscope confirms that the average grain diameter of this nano particle is 3.0nm, and distribution is less than 1.5nm.Its oxidation-reduction potential of cyclic voltammetry experiment proof is 0.5V.
Embodiment 3
The mol ratio of chloroplatinic acid and 2-mercaptoquinoline is 1: 4, and the mol ratio of chloroplatinic acid and natrium citricum is 1: 20, and vacuum distillation temperature is 50 ℃, and other condition is identical with embodiment 1.Transmission electron microscope confirms that the average grain diameter of this nano particle is 1.7nm, and distribution is less than 1.5nm.Its oxidation-reduction potential of cyclic voltammetry experiment proof is-1.2V.
Embodiment 4
The mol ratio of palladium bichloride and 2-mercaptoquinoline is 1: 1, and the mol ratio of palladium bichloride and four octyl group amine bromides is 1: 1, and the mol ratio of palladium bichloride and sodium borohydride is 1: 10, and vacuum distillation temperature is 40 ℃, and other conditions are identical with embodiment 1.Transmission electron microscope confirms that the particle diameter of this nano particle is 2.9nm, and the oxidation-reduction potential that cyclic voltammetric confirms it is at-1.2V.
Embodiment 5
Gold chloride and 1-(1, the 3-dimercaptopropane) anthracene-9, the mol ratio of 10-diketone is 1: 1, and the mol ratio of gold chloride and sodium borohydride is 1: 15, and other conditions are identical with embodiment 1.Transmission electron microscope confirms that the average grain diameter of this nano particle is 3.0nm, and cyclic voltammetry experiment confirms that its oxidation-reduction potential is-1.0V.
Embodiment 6
Silver nitrate and 1-(1, the 3-dimercaptopropane) anthracene-9, the mol ratio of 10-diketone is 1: 3, and the mol ratio of silver nitrate and four octyl group ammonium chlorides is 1: 2, and vacuum distillation temperature is 45 ℃.Other condition is identical with embodiment 1.Transmission electron microscope confirms that the average grain diameter of this nano particle is 1.6nm.The oxidation-reduction potential that cyclic voltammetric confirms it is at-1.0V.
Embodiment 7
Palladium bichloride and 1-(1, the 3-dimercaptopropane) anthracene-9, the mol ratio of 10-diketone is 1: 2, and the mol ratio of palladium bichloride and four octyl group ammonium chlorides is 1: 1, and the mol ratio of palladium bichloride and natrium citricum is 1: 15, and vacuum distillation temperature is 50 ℃.Other conditions are identical with embodiment 1.Transmission electron microscope confirms that the average grain diameter of this nano particle is 2.2nm.The oxidation-reduction potential that cyclic voltammetric confirms it is at-1.0V.
Claims (1)
1. the preparation method with metal nanoparticle of redox active is with gold chloride, chloroplatinic acid, and silver nitrate or palladium bichloride are predecessor, and be soluble in water, wiring solution-forming, concentration≤0.01mol/l; Wherein the mol ratio of predecessor and stabilizing agent is 1: 1～4; Phase transfer catalyst four octyl group amine bromides or four octyl group ammonium chlorides are dissolved in the toluene, are made into the phase transfer catalysis (PTC) agent solution, the mol ratio that makes predecessor and phase transfer catalyst is 1: 1～2; Borane reducing agent sodium hydride or natrium citricum is soluble in water, be made into reductant solution, the mol ratio that makes predecessor and reducing agent is 1: 10～15, under the room temperature, the phase transfer catalysis (PTC) agent solution is added in the predecessor that stirs, and under the effect of phase transfer catalyst, predecessor is transferred in the toluene organic facies; The toluene organic facies is separated, stabilizing agent is added above-mentioned organic facies slowly, stir; Then reducing agent is added organic facies rapidly, continue to stir; The organic facies that obtains in the mixed solution is separated, remove toluene solvant 30 ℃～50 ℃ following decompression distillation, obtain the product of black, utilize a large amount of water, ethanol, the above-mentioned product of washing that acetone is continuous, remove excessive stabilizing agent and phase transfer catalyst, obtain the metal nanoparticle of diameter between 1.7nm～3.3nm, it is characterized in that described stabilizing agent is 4-ferrocene benzenethiol, 2-mercaptoquinoline or 1-(1, the 3-dimercaptopropane) anthracene-9, the 10-diketone.
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| CN100431749C (en) * | 2005-07-29 | 2008-11-12 | 江征平 | Nano metal particles in high density and preparation method |
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| CN100431749C (en) * | 2005-07-29 | 2008-11-12 | 江征平 | Nano metal particles in high density and preparation method |
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