CN102642809B - Organic nanowire/metal nano particle composite nano material and preparation method thereof - Google Patents
Organic nanowire/metal nano particle composite nano material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic nanowire/metal nano particle composite nano material and a preparation method thereof. The method includes utilizing a solution configured by tetrahydrofuran/N, an N-dimethyl formamide mixed solvent and a schiff base or metal phthalocyanine compound, inducing growth of the one-dimensional organic nanowire through a solvent evaporation method, and adding a reducing agent boron hydride compound in a suspension system of the one-dimensional organic nanowire and a metal salt solution so as to obtain a one-dimensional composite nano structure. Simultaneously, by changing concentration of the metal salt solution, the one-dimensional composite nano structure with different metal nano particle deposition amount can be achieved. The preparation method is simple and easy to perform, achieves high-level assembly of a pure organic nano structure, enables the pure organic nano structure to be generated into a complex composite structure.
Description
Technical field
The present invention relates to a kind of nano composite material and preparation method thereof, more specifically, the present invention relates to a kind of organic nano line/metal nanoparticle composite nano materials and preparation method thereof.
Background technology
Due in some fields for example in bio-separation, bio-sensing, catalysis, commaterial need to be brought into play several functions, the nano material of one-component is difficult to meet this demand, by preparing multi-component nano material, obtain broad interest (the Colloidal Hybrid Nanostructures:A New Type of Functional Materials that multifunctional material has caused scientists, Costi Ronny, Saunders Aaron E., Banin Uri, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010 4878-4897; Self-directed Self-assembly of Nanoparticle/Copolymer Mixtures, Lin Y, Boker A, He JB, NATURE, 2005,55-59.).Consider that organic molecule kind is many, functional group is abundant, the character such as the photo electric of the cheap preparation of one dimension organic nanostructure, pliability, excellence, electric conductivity, integrate the performances such as special optical, electrical, the magnetic of inorganic nano material, catalysis, in fields such as optics, catalysis, stored energy and conversion, micro-nano electronic device, biomedicine, bio-sensings, have huge potential application.Therefore, developing new one dimension organic nano material/metal nanometer composite material has great importance.
One-dimensional inorganic nanostructured metal nano particle composite construction is generally studied (Poly (vinylpyrrolidone)-Modified Graphite Carbon Nanofibers as Promising Supports for PtRu Catalystsin Direct Methanol Fuel Cells, Hsin Yu Lin; Hwang Kuo Chu; Yeh Chuin-Tih, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007,9999-10010; Observing Catalysis through the Agency of the Participating Electrons:Surface-Chemistry-Induced Current ChangesinaTin Oxide Nanowire Decorated with Silver, Chen X.H.; Moskovits M., NANO LETTERS, 2007,807-812.), the report about one dimension organic nanostructure/metal nanoparticle composite construction still and for several still lacks now.
And, while generally preparing composite construction with strong reductant reducing metal ions such as sodium borohydrides, conventionally want chemical treatment substrate or add surfactant, to improve the dispersiveness of metallic particles.
The present invention, just based on this research background, proposes the composite construction of the organic nano wire/metal nanoparticle of a kind of simple preparation.
Summary of the invention
First technical problem that the present invention will solve is to provide a kind of organic nano line/metal nanoparticle composite nano materials.
Second technical problem that the present invention will solve is to provide a kind of preparation method of organic nano line/metal nanoparticle composite nano materials.The solution that utilizes oxolane/DMF mixed solvent and schiff bases or metal phthalocyanine compound to configure, induces the growth of one dimension organic nano line by solvent evaporation method; To being suspended of one dimension organic nano line and metal salt solution, in system, add borane reducing agent sodium hydride again, thereby obtain one-dimensional composite nano structure.By changing the concentration of metal salt solution, can realize the one-dimensional composite nano structure of different metal nanoparticle deposition amount.
For solving above-mentioned first technical problem, a kind of organic nano line/metal nanoparticle of the present invention composite nano materials, wherein organic nano line is schiff bases or metal phthalocyanine compound;
The metal nanoparticle size being adsorbed on organic nano line is 20-50nm, and the spacing between metallic particles is 10-100nm.
Further, described schiff bases is that double salicylaldehyde o-phenylenediamine closes zinc (II); Described metal phthalocyanine compound is Phthalocyanine Zinc, CuPc; Described metal is silver, gold or platinum; Described organic nano line length is more than 100 μ m, and diameter is 100-200nm.
For solving above-mentioned second technical problem, the preparation method of a kind of organic nano line/metal nanoparticle of the present invention composite nano materials, comprises the following steps:
1) prepare organic nano wire
Oxolane/DMF mixed solvent and schiff bases or metal phthalocyanine compound are configured to solution, make solvent evaporates, obtain organic nano line; Adding of higher boiling DMF, the speed of reduction solvent evaporates, is beneficial to nano wire radial direction and fully grows, thereby obtain the organic nano line compared with big L/D ratio;
2) adsorption of metal ions
The organic nano line having prepared is dispersed in the metal salt solution that concentration is 0.5～10mmol/L.The concentration of slaine is larger, and the metal deposition obtaining is more, and the spacing of metallic is less.Stir, mixing time is more than or equal to 1 day, obtains organic nano line/slaine suspension; The mass ratio of described organic nano line and slaine is 2: 1～10; In order to ensure metallic, can dispersedly be adsorbed on organic nano surface, guarantee to stir the time long enough of organic nano line/slaine suspension;
3) one-dimensional composite nano material preparation
By hydroboron solution and step 2) in organic nano line/slaine suspension mix; In described hydroboron and described suspension, the mol ratio of slaine is 1: 200～600, and incorporation time is more than or equal to 0.5 day, obtains organic nano line/metal nanoparticle composite nano materials.In order to obtain the silver nano-grain sedimentary deposit of suitable dimension, spacing, add after reducing agent the nucleating growth time that guarantee fund's metal particles is enough.
Further, step 1) oxolane/N described in, oxolane and N in dinethylformamide mixed solvent, dinethylformamide (THF: volume ratio DMF) is 2: 3, the selection of this ratio can make the draw ratio of nano wire of preparation larger, can better realize technique effect of the present invention.
Further, schiff bases step 1) is that double salicylaldehyde o-phenylenediamine closes zinc (II); Described metal phthalocyanine compound is Phthalocyanine Zinc, CuPc; The concentration of described solution is 15～30mg/L.
Further, the metal salt solution step 2) is silver nitrate, gold chloride, chloroplatinic acid.
Further, step 2) described in, stir as magnetic agitation, mixing time is 2 days.
Further, step 2) in, resulting organic nano line length is more than 100 μ m, and diameter is 100-200nm.The draw ratio of the organic nano line of preparation is larger, and the ability that forms composite is stronger.
Further, step 3), hydroboron is sodium borohydride or potassium borohydride; The concentration of described hydroboron is 0.1～1mol/L.
Further, step 3) in the organic nano line/metal nanoparticle composite nano materials obtaining in, the metallic particles of organic nano line surface deposition size 20-50nm, the spacing between metallic particles is 10-100nm.
Beneficial effect of the present invention
1. the present invention obtains the organic nano line compared with big L/D ratio by simple solvent evaporation method.
2. the present invention, by simple reducing agent method, can obtain the composite construction that nanowire surface is uniformly distributed silver-colored particle at normal temperatures, convenient and swift.
3. the present invention has realized compound on nanoscale, in the situation that not needing carry out in advance chemical treatment and add surfactant, makes the silver-colored particle can reach uniform dispersion, and does not form aggregate structure so that granule-morphology changes.
Accompanying drawing explanation
Fig. 1. embodiment 1 double salicylaldehyde o-phenylenediamine closes ESEM (SEM) photo of zinc (II) nano wire.
Fig. 2. embodiment 2 double salicylaldehyde o-phenylenediamines close ESEM (SEM) photo of zinc (II) nano wire/silver nano-grain composite nanostructure.
Fig. 3. embodiment 3 double salicylaldehyde o-phenylenediamines close ESEM (SEM) photo of zinc (II) nano wire/silver nano-grain composite nanostructure.
Fig. 4. embodiment 4 double salicylaldehyde o-phenylenediamines close ESEM (SEM) photo of zinc (II) nano wire/silver nano-grain composite nanostructure.
Fig. 5. ESEM (SEM) photo of embodiment 5 Phthalocyanine Zinc nano wire/silver nano-grain composite nanostructures.
Fig. 6. ESEM (SEM) photo of embodiment 6 CuPc nano wire/silver nano-grain composite nanostructures.
Fig. 7. the comparison diagram that silver particles is disperseed.
The specific embodiment
Organic solvent Jun Cong Beijing chemical reagents corporation used in experiment buys, and before use, is not for further processing.
Embodiment 1:
Prepare organic nano wire
The organic matter that the present embodiment is used closes zinc (II) (Zn (salophen)) for double salicylaldehyde o-phenylenediamine, synthetic method is with reference to (A.L.Singer, D.A.Atwood, Inorganica Chimica Acta 1990,277,157～162), its structure is suc as formula shown in (1):
The THF/DMF mixed solvent that configuration volume ratio is 2: 3, this mixed solvent and Zn (salophen) are configured to the solution of organic compound that concentration is 20mg/L, by solvent evaporation method, induce organic molecule to assemble, after treating solvent evaporates, collect sample. more than in Fig. 1, the length of visible nano wire can reach 100 μ m, the about 150nm of diameter.
Embodiment 2:
The nano wire of preparing according to the method for embodiment 1, is dispersed in 10mL silver nitrate (1mM) solution magnetic agitation 2 days by this nano wire of 2mg, and adds fast wherein 100 μ L, the sodium borohydride reduction agent solution of 0.5mM, and continuous stirring 1 day.Product is centrifugal through three times, obtain in one-dimensional composite nano structure, the about 20nm of silver-colored granular size, between the about 80nm of spacing.As shown in Figure 2.
Embodiment 3:
Repeat embodiment 2, its difference is only that silver nitrate concentration is 3mM, in the one-dimensional composite nano structure obtaining, the about 20nm of silver-colored granular size, between the about 50nm of spacing.As shown in Figure 3.
Embodiment 4:
Repeat embodiment 2, its difference is only that silver nitrate concentration changes 5mM into, in the one-dimensional composite nano structure obtaining, the about 20nm of silver-colored granular size, between the about 20nm of spacing.As shown in Figure 4.
Embodiment 5:
The organic matter that the present embodiment is used is Phthalocyanine Zinc (Zinc phthalocyanine), and its structure is suc as formula shown in (2).
The THF/DMF mixed solvent that configuration volume ratio is 2: 3, this mixed solvent and Zincphthalocyanine are configured to the solution of organic compound that concentration is 20mg/L, by solvent evaporation method, induce organic molecule to assemble, after treating solvent evaporates, collect sample. 2mg Phthalocyanine Zinc nano wire is dispersed in 10mL silver nitrate (8mM) solution to magnetic agitation 2 days, and add fast wherein 100 μ L, the sodium borohydride reduction agent solution of 0.5mM, and continuous stirring 1 day.Product is centrifugal through three times, obtain in one-dimensional composite nano structure, the about 20nm of silver-colored granular size, between the about 20nm of spacing.As shown in Figure 5.
Embodiment 6:
Repeat embodiment 5, only organic matter used is changed into CuPc (Copper phthalocyanine).The 1-dimention nano composite construction obtaining as shown in Figure 6.
Embodiment 7:
1) the THF/DMF mixed solvent that configuration volume ratio is 2: 3, is configured to by mixed solvent and CuPc the solution that concentration is 15mg/L, makes solvent evaporates, obtains length to be more than 100 μ m the organic nano line that diameter is 100nm;
2) the organic nano line having prepared being dispersed in to concentration is in 0.5mmol/L liquor argenti nitratis ophthalmicus, stirs 1 day, obtains organic nano line/silver nitrate suspension; The mass ratio of described organic nano line and silver nitrate is 2: 1;
3) the hydroboron solution and the step 2 that by concentration, are 0.1mol/L) in organic nano line/silver nitrate suspension mix; The mol ratio of described hydroboron solution and described suspension is 1: 300, and incorporation time is 0.5 day, obtains organic nano line/silver nano-grain composite nano materials, and silver-colored granular size is 50nm, and silver-colored intergranular spacing is 10nm.
Embodiment 8:
1) the THF/DMF mixed solvent that configuration volume ratio is 2: 3, is configured to by mixed solvent and CuPc the solution that concentration is 30mg/L, makes solvent evaporates, obtains length to be more than 100 μ m the organic nano line that diameter is 200nm;
2) the organic nano line having prepared is dispersed in the liquor argenti nitratis ophthalmicus that concentration is 10mmol/L, stirs 1 day, obtain organic nano line/silver nitrate suspension; The mass ratio of described organic nano line and silver nitrate is 2: 10;
3) the hydroboron solution and the step 2 that by concentration, are 1mol/L) in organic nano line/silver nitrate suspension mix; The mol ratio of described hydroboron solution and described suspension is 1: 500, and incorporation time is 0.5 day, obtains organic nano line/silver nano-grain composite nano materials, and silver-colored granular size is about 50nm, and silver-colored intergranular spacing is about 100nm.
Embodiment 9:
Repeat embodiment 8, its difference is only to add gold chloride, obtains organic nano line/gold nano grain composite nano materials, and gold grain size is for being about 50nm, and the spacing between gold grain is about 100nm.
Embodiment 10:
Repeat embodiment 8, its difference is only to add chloroplatinic acid; Obtain organic nano line/gold nano grain composite nano materials, platinum grain size is 50nm, and the spacing between platinum grain is 100nm.
Fig. 7 is for coming from J Mater Sci (2009) 44:3983-3990, and exercise question is the picture that the silver particles of the document of Antifungal efficiency of corona pretreated polyester and polyamide fabrics loaded with Ag nanoparticles is disperseed.Contrast can find out, the silver particles in Fig. 7 is dispersed not as the present invention, and has to a certain extent clustering phenomena.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give all embodiments exhaustive.Every still row in protection scope of the present invention of apparent variation that technical scheme of the present invention extends out or change that belong to.
Claims (10)
1. organic nano line/metal nanoparticle composite nano materials, is characterized in that, wherein organic nano line is metal phthalocyanine compound;
The metal nanoparticle size being adsorbed on organic nano line is 20-50nm, and the spacing between metallic particles is 10-100nm.
2. composite nano materials according to claim 1, is characterized in that, described metal phthalocyanine compound is Phthalocyanine Zinc, CuPc; Described metal is silver, gold or platinum; Described organic nano line length is more than 100 μ m, and diameter is 100-200nm.
3. a preparation method for organic nano line/silver nano-grain composite nano materials as claimed in claim 1, is characterized in that, comprises the following steps:
1) prepare organic nano wire
Oxolane/DMF mixed solvent and metal phthalocyanine compound are configured to solution, make solvent evaporates, obtain organic nano line;
2) adsorption of metal ions
The organic nano line preparing in step 1) is dispersed in the metal salt solution that concentration is 0.5～10mmol/L, stirs, mixing time is more than or equal to 1 day, obtains organic nano line/slaine suspension; The mass ratio of described organic nano line and slaine is 2:1～10;
3) one-dimensional composite nano material preparation
By hydroboron solution and step 2) in organic nano line/slaine suspension mix; In described hydroboron and described suspension, the mol ratio of slaine is 1:200～600, and incorporation time is more than or equal to 0.5 day, obtains organic nano line/metal nanoparticle composite nano materials.
4. method according to claim 3, is characterized in that, in the mixed solvent of oxolane/DMF described in step 1), the volume ratio of oxolane and DMF (THF:DMF) is 2:3.
5. method according to claim 3, is characterized in that, metal phthalocyanine compound described in step 1) is Phthalocyanine Zinc, CuPc; The concentration of described solution is 15～30mg/L.
6. method according to claim 3, is characterized in that step 2) described in metal salt solution be silver nitrate, gold chloride or chloroplatinic acid.
7. method according to claim 3, is characterized in that step 2) described in stir as magnetic agitation, mixing time is 2 days.
8. method according to claim 3, is characterized in that step 2) in resulting organic nano line length be more than 100 μ m, diameter is 100-200nm.
9. method according to claim 3, is characterized in that, in step 3), hydroboron is sodium borohydride or potassium borohydride; The concentration of described hydroboron is 0.1～1mol/L.
10. method according to claim 3, it is characterized in that, in the organic nano line/metal nanoparticle composite nano materials obtaining in step 3), the metallic particles of organic nano line surface deposition size 20-50nm, the spacing between metallic particles is 10-100nm.
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