CN101081435A - Bionics method for preparation of precious metal simple substance nanometer material - Google Patents
Bionics method for preparation of precious metal simple substance nanometer material Download PDFInfo
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- CN101081435A CN101081435A CN 200710042925 CN200710042925A CN101081435A CN 101081435 A CN101081435 A CN 101081435A CN 200710042925 CN200710042925 CN 200710042925 CN 200710042925 A CN200710042925 A CN 200710042925A CN 101081435 A CN101081435 A CN 101081435A
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Abstract
The bionic process of preparing nanometer simple noble metal substance material includes the following steps: soaking marketed mung bean sprout in water for 2-4 hr; compounding noble metal ion solution and reductant solution of 0.01-0.2 mol/l separately; soaking the mung bean sprout first in the noble metal ion solution at normal temperature for 6-36 hr; taking out and soaking in the reductant solution at normal temperature for 6-36 hr; ultrasonically treating the mung bean sprout in anhydrous alcohol to separate out the product in the surface of mung bean sprout; dissecting the mung bean sprout and separating out the product in the inner surface and vascular system; and collecting the product as the required nanometer simple noble metal substance material. The process is simple, universal, environment friendly and low in cost, and possesses excellent industrial application foreground.
Description
Technical field
The present invention relates to a kind of bionics method for preparation of precious metal simple substance nanometer material.
Background technology
Gold, silver and platinum family element (platinum, palladium, rhodium, iridium, osmium, ruthenium) are called as noble metal, particularity because of atomic structure, show excellent physicochemical properties, become class particulate metal that effect is unique in the industrial circle, use value is high, do not replace, spread all over nearly all industries such as electronics, chemical industry, medicine, machinery, the energy, metallurgy, pottery and traffic.The employed noble metal of these industries all is deep processed product usually, is about to precious metal simple substance or compound by a series of process, and its physics or chemical form are changed, and becomes the process of the objects made from precious metals that use value is more arranged.
Nano material be a kind of be the material of the multiple different-shape structural system such as spherical, bar-shaped, wire, tubulose, lath-shaped and dendroid of yardstick with nanometer (1/1000000000th meter).Because constitute the particle of this material and have that small-size effect, skin effect are grand, fundamental characteristics such as quantum size effect and macro quanta tunnel effect, this material has good photoelectric characteristic, heat conductivity, magnetism characteristic, mechanical property and catalytic performance etc., and they can be used as the construction unit of electronic devices and components such as photoelectron of new generation, electrochemistry, motor machine.
The noble metal nanometer material that the deep processing that utilizes nanometer technology to carry out noble metal obtains is extremely people's concern now.Noble metal nanometer material is meant the exploitation of utilization nanometer technology and produces objects made from precious metals, obtain size below the 100nm new material that contains noble metal of (or containing the corresponding size nanophase), these new materials have very big-difference with traditional precious metal material in nature at optics, electricity, acoustics, magnetics and mechanics etc.Precious metal simple substance has a purposes widely in that catalyst is industrial, and precious metal simple substance nanometer material is because its particular structure has excellent more performance and wide application prospect in the catalyst application facet.There has been the human distinct methods to prepare precious metal simple substance nanometer material before this, as people such as Zhang Zhijun in the organic media decahydronaphthalenes, with sodium metal, silver nitrate and enuatrol is initiation material, make sodium metal and silver nitrate generation displacement reaction by ultrasonic radiation, the Ag nanoparticle that has prepared the oleic acid finishing, average-size is 10nm, distribution uniform.People such as Lanzhou-Xinjiang wise man adopt oxalic acid reduction higher concentration HAuCl
4The method of solution is done in protectant aqueous solution at PVP, has prepared the aurosol of granularity average out to 20nm～30nm and high degree of dispersion.People such as Du Yu button utilize suction hydrogen to restore method, carry out progressively reduction reaction, have synthesized the Pt nanoparticle of a series of average grain diameters from 1.8nm to 14.1nm.
Nanometer technology combines with the noble metal deep processing, and these conventional industries of noble metal deep processing are transformed, and has widened the scope of noble metal deep processing, has increased many new noble metal deep processed products, and industrialization prospect is fine.
Summary of the invention
The object of the present invention is to provide a kind of bionics method for preparation of precious metal simple substance nanometer material.
In order to achieve the above object, the present invention is performed such.Through years of researches, it has been recognized that it is masterpiece by the biomineralization of living body biological under cell control that occurring in nature has a large amount of mineral, be the nano material of high-quality.As everyone knows, the biogenic mineral that occurring in nature forms is compound mostly, directly seldom obtains the simple substance material by the control of living body biological cell.And under laboratory condition, can accomplish fully guaranteeing to carry out the preparation of simple substance material by chemical reaction under the normal effect of living body biological.Thus, we consider under laboratory environment, utilize living body biological film (cell membrane) that processes such as the absorption of ion, transmission are realized adjusting control to chemical reaction, and simulation biomineralization process is in the hope of obtaining the product of nanostructured.
The bionics method for preparation of the precious metal simple substance nanometer material that the present invention proposes, utilize the different living body biological film of external and internal compositions as template, under the room temperature normal pressure, pass through the control action of living body biological film, through simple chemical reaction, under aqueous environment, thereby prepare the different precious metal simple substance nanometer material of structure, concrete preparation process is as follows:
(1) get commercially available mung bean sprouts, be soaked in water 2-4 hour, clean, stand-by;
(2) preparing molar concentration respectively is 0.01～0.2 molL
-1Precious metal ion solution and molar concentration be 0.01～0.2molL
-1Reductant solution; Mung bean sprouts with step (1) gained is soaked in the precious metal ion solution earlier, soaks at normal temperatures and pressures and supports 6 hours-36 hours; Take out mung bean sprouts, outer surface is cleaned with deionized water, it is changed in the reductant solution soak then, soaks at normal temperatures and pressures and supports 6 hours-36 hours;
(3) step (2) gained mung bean sprouts is cleaned its surface with deionized water, in absolute ethyl alcohol, mung bean sprouts is carried out ultrasonic processing, isolate the product of mung bean sprouts outer surface, washing, products therefrom 1 is scattered in absolute ethyl alcohol;
(4) mung bean sprouts of step (3) being isolated behind the product 1 is cut open, isolates the product on mung bean sprouts inner surface and skeleton surface, washing, and products therefrom 2 is scattered in the absolute ethyl alcohol;
(5) use transmission electron microscope (TEM) to observe and X-ray powder diffraction (XRD) sign respectively step (3) products therefrom 1 and step (4) products therefrom 2, products therefrom 1 and product 2 are nanometer materials, are products obtained therefrom of the present invention.
Among the present invention, described precious metal ion solution is AgNO
3, Ag
2SO
4, HAuCl
4, H
2PdCl
4Or H
2PtCl
4Deng in any.
Among the present invention, described reducing agent is ascorbic acid, KBH
4, NaBH
4, in hydrazine hydrate, trisodium citrate or sodium oxalate etc. any.
Among the present invention, be soaked in water described in the step (1) and adopt running water and distilled water successively to soak in regular turn.
Among the present invention, washing described in step (3) and the step (4) can adopt deionized water, acetone and absolute ethyl alcohol alternately to clean, and generally washs 2-6 time.
The present invention has following advantage:
1. preparation method of the present invention is simple, need not exacting terms and high equipment, also is a kind of effective trial for the comprehensive utilization plant resources simultaneously, environmentally safe, and with low cost, the futurity industry prospect of production is good.
2. preparation method of the present invention is applicable to the preparation of all precious metal simple substances, has universality.
3. the inventive method can be prepared two kinds of different precious metal simple substance nanometer materials of structure synchronously on a kind of living body biological film, is that template is prepared the perfect of nano material method.
Description of drawings
Fig. 1 is the product 1 of the embodiment of the invention 1 gained Nano Silver product and transmission electron microscope (TEM) phenogram of product 2.Wherein: being the TEM figure of product 1 (a), (b) being the TEM partial enlarged drawing of product 1, (c) is the TEM figure of product 2, (d) the TEM partial enlarged drawing of product 2.Find through transmission electron microscope observation, product is the structure for being made of nanoparticle all, find that simultaneously the nanostructured of product 1 and 2 has nothing in common with each other again: product 1 is by better the reunite nanosphere piece of defective tightness of the dispersion that nano particle is assembled into, the nano particle average diameter that wherein constitutes reunion ball piece is about 10～30nm, and the diameter of the ball piece that is constituted is mostly between 60～80 nanometers; Product 2 is the nano-superstructures that are rendered as " pine needle " shape by the nano particle assembling more closely, this superstructure that makes discovery from observation is to be assembled into " nanometer rods " earlier through nano particle, " nanometer rods " is assembled into " nanometer tree branches " again, and last " nanometer tree branches " reunited and be " nanometer pine needle ".
Fig. 2 is the product 1 of inventive embodiments 1 gained Nano Silver product and the XRD figure of product 2.Wherein, (a) being the XRD figure of product 1, (b) is the XRD figure of product 2.From XRD figure, as can be known, do not have assorted peak in the collection of illustrative plates of products therefrom, illustrate that product is simple substance silver; And diffraction maximum all has certain broadening phenomenon, and this is the result of nanometer small-size effect.Product 1 and 2 is also different as can be seen in the XRD figure: product 1 is more obvious than product 2 diffraction maximum broadenings, illustrates that the particle diameter of product 1 is littler with respect to product 2, and this also confirms mutually with the result of transmission electron microscope observation; In addition, product 2 is stronger relatively in the diffraction maximum of (200) face, and these explanation product 2 structure growth have certain orientation, the formation of this its " nanometer pine needle " superstructure of also coincideing.
The specific embodiment
Embodiment 1:
At first, get commercially available mung bean sprouts, it was successively soaked 1 hour with running water, distilled water, washes clean, stand-by.
Then, preparation 200ml (0.2molL
-1) AgNO
3Solution and 200ml (0.2molL
-1) Vc (ascorbic acid) aqueous solution (it is pure that used reagent is analysis, and the back together), place two 250ml beakers respectively.After above-mentioned commercially available mung bean sprouts through washing is cleaned with deionized water again, several bean sprouts root vertically put into down fill AgNO
3In the beaker of solution, and make its rhizome portion all immerse solution, only expose blade.Take out after at room temperature soaking foster 6h, rinse out the AgNO of mung bean sprouts outer surface with deionized water
3Solution changes it then and immerses in the Vc solution, at room temperature soaks equally and supports 12h.
Take out mung bean sprouts, with deionized water that its surface washing is clean, in absolute ethyl alcohol, mung bean sprouts is carried out ultrasonic processing, isolate the product of bean sprouts outer surface, successively alternately clean 2-3 time, disperse product 1 with absolute ethyl alcohol at last with deionized water, acetone, absolute ethyl alcohol.
Again above-mentioned bean sprouts through ultrasonic processing is cut open, isolated the product on bean sprouts inner surface and skeleton surface, successively clean, disperse product 2 with absolute ethyl alcohol at last with deionized water, acetone, absolute ethyl alcohol.
As depicted in figs. 1 and 2, products therefrom 1 and product 2 characterize with transmission electron microscope observation and X-ray powder diffraction respectively, and products obtained therefrom is a Nano Silver.
Embodiment 2:
At first, get commercially available mung bean sprouts, it was successively soaked 1 hour with running water, distilled water, washes clean, stand-by.
Then, preparation 200ml (0.01molL
-1) Ag
2SO
4Solution and 200ml (0.01molL
-1) KBH
4Solution places two 250ml beakers respectively.After above-mentioned commercially available mung bean sprouts through washing is cleaned with deionized water again, several bean sprouts root vertically put into down fill Ag
2SO
4In the beaker of solution, and make its rhizome portion all immerse solution, only expose blade.Take out after at room temperature soaking foster 36h, rinse out the Ag of mung bean sprouts outer surface with deionized water
2SO
4Solution changes it then and immerses KBH
4In the solution, at room temperature soak equally and support 24h.
Take out mung bean sprouts, with deionized water that its surface washing is clean, in absolute ethyl alcohol, mung bean sprouts is carried out ultrasonic processing, isolate the product of bean sprouts outer surface, successively alternately clean 2-4 time, disperse product 1 with absolute ethyl alcohol at last with deionized water, acetone, absolute ethyl alcohol.
Again above-mentioned bean sprouts through ultrasonic processing is cut open, isolated the product on bean sprouts inner surface and skeleton surface, successively clean, disperse product 2 with absolute ethyl alcohol at last with deionized water, acetone, absolute ethyl alcohol.
Products therefrom 1 and product 2 characterize with transmission electron microscope observation and X-ray powder diffraction respectively, and products obtained therefrom is a Nano Silver.
Embodiment 3:
At first, get commercially available mung bean sprouts, it was successively soaked 1 hour with running water, distilled water, washes clean, stand-by.
Then, preparation 200ml (0.02molL
-1) HAuCl
4Solution and 200ml (0.02molL
-1) the sodium oxalate aqueous solution, place two 250ml beakers respectively.After above-mentioned commercially available mung bean sprouts through washing is cleaned with deionized water again, several bean sprouts root vertically put into down fill HAuCl
4In the beaker of solution, and make its rhizome portion all immerse solution, only expose blade.Take out after at room temperature soaking foster 24h, rinse out the HAuCl of mung bean sprouts outer surface with deionized water
4Solution changes it then and immerses in the sodium oxalate solution, at room temperature soaks equally and supports 12h.
Take out mung bean sprouts, with deionized water that its surface washing is clean, in absolute ethyl alcohol, mung bean sprouts is carried out ultrasonic processing, isolate the product of bean sprouts outer surface, successively alternately clean 5-6 time, disperse product 1 with absolute ethyl alcohol at last with deionized water, acetone, absolute ethyl alcohol.
Again above-mentioned bean sprouts through ultrasonic processing is cut open, isolated the product on bean sprouts inner surface and skeleton surface, successively clean, disperse product 2 with absolute ethyl alcohol at last with deionized water, acetone, absolute ethyl alcohol.
Products therefrom 1 and product 2 characterize with transmission electron microscope observation and X-ray powder diffraction respectively, and products obtained therefrom is a nm of gold.
Embodiment 4:
At first, get commercially available mung bean sprouts, it was successively soaked 1 hour with running water, distilled water, washes clean, stand-by.
Then, preparation 200ml (0.05molL
-1) H
2PdCl
4Solution and 200ml (0.05molL
-1) citric acid three sodium solution, place two 250ml beakers respectively.After above-mentioned commercially available mung bean sprouts through washing is cleaned with deionized water again, several bean sprouts root vertically put into down fill H
2PdCl
4In the beaker of solution, and make its rhizome portion all immerse solution, only expose blade.Take out after at room temperature soaking foster 24h, rinse out the H of mung bean sprouts outer surface with deionized water
2PdCl
4Solution changes it then and immerses in the citric acid three sodium solution, at room temperature soaks equally and supports 12h.
Take out mung bean sprouts, with deionized water that its surface washing is clean, in absolute ethyl alcohol, mung bean sprouts is carried out ultrasonic processing, isolate the product of bean sprouts outer surface, successively alternately clean 3-5 time, disperse product 1 with absolute ethyl alcohol at last with deionized water, acetone, absolute ethyl alcohol.
Again above-mentioned bean sprouts through ultrasonic processing is cut open, isolated the product on bean sprouts inner surface and skeleton surface, successively clean, disperse product 2 with absolute ethyl alcohol at last with deionized water, acetone, absolute ethyl alcohol.
Products therefrom 1 and product 2 characterize with transmission electron microscope observation and X-ray powder diffraction respectively, and products obtained therefrom is the nanometer palladium.
Embodiment 5:
At first, get commercially available mung bean sprouts, it was successively soaked 1 hour with running water, distilled water, washes clean, stand-by.
Then, preparation 200ml (0.15molL
-1) H
2PtCl
4Solution and 200ml (0.15molL
-1) KBH
4Solution places two 250ml beakers respectively.After above-mentioned commercially available mung bean sprouts through washing is cleaned with deionized water again, several bean sprouts root vertically put into down fill H
2PtCl
4In the beaker of solution, and make its rhizome portion all immerse solution, only expose blade.Take out after at room temperature soaking foster 18h, rinse out the H of mung bean sprouts outer surface with deionized water
2PtCl
4Solution changes it then and immerses KBH
4In the solution, at room temperature soak equally and support 18h.
Take out mung bean sprouts, with deionized water that its surface washing is clean, in absolute ethyl alcohol, mung bean sprouts is carried out ultrasonic processing, isolate the product of bean sprouts outer surface, successively alternately clean 3-4 time, disperse product 1 with absolute ethyl alcohol at last with deionized water, acetone, absolute ethyl alcohol.
Again above-mentioned bean sprouts through ultrasonic processing is cut open, isolated the product on bean sprouts inner surface and skeleton surface, successively clean, disperse product 2 with absolute ethyl alcohol at last with deionized water, acetone, absolute ethyl alcohol.
Products therefrom 1 and product 2 characterize with transmission electron microscope observation and X-ray powder diffraction respectively, and products obtained therefrom is a nanometer platinum.
Claims (5)
1, a kind of bionics method for preparation of precious metal simple substance nanometer material is characterized in that concrete preparation process is as follows:
(1) get commercially available mung bean sprouts, be soaked in water 2-4 hour, clean, stand-by;
(2) preparing molar concentration respectively is 0.01～0.2molL
-1Precious metal ion solution and molar concentration be 0.01～0.2molL
-1Reductant solution; Mung bean sprouts with step (1) gained is soaked in the precious metal ion solution earlier, soaks at normal temperatures and pressures and supports 6 hours-36 hours; Take out mung bean sprouts, outer surface is cleaned with deionized water, it is changed in the reductant solution soak then, soaks at normal temperatures and pressures and supports 6 hours-36 hours;
(3) step (2) gained mung bean sprouts is cleaned its surface with deionized water, in absolute ethyl alcohol, mung bean sprouts is carried out ultrasonic processing, isolate the product of mung bean sprouts outer surface, washing, products therefrom 1 is scattered in absolute ethyl alcohol;
(4) mung bean sprouts of step (3) being isolated behind the product 1 is cut open, isolates the product on mung bean sprouts inner surface and skeleton surface, washing, and products therefrom 2 is scattered in the absolute ethyl alcohol;
(5) step (3) products therefrom 1 and step (4) products therefrom 2 are characterized with transmission electron microscope observation and X-ray powder diffraction respectively, products therefrom 1 and product 2 are nanometer materials, are products obtained therefrom of the present invention.
2, the bionics method for preparation of precious metal simple substance nanometer material according to claim 1 is characterized in that described precious metal ion solution is AgNO
3, Ag
2SO
4, HAuCl
4, H
2PdCl
4Or H
2PtCl
4In any.
3, the bionics method for preparation of precious metal simple substance nanometer material according to claim 1 is characterized in that described reducing agent is ascorbic acid, KBH
4, NaBH
4, in hydrazine hydrate, trisodium citrate or the sodium oxalate any.
4, the bionics method for preparation of precious metal simple substance nanometer material according to claim 1 is characterized in that being soaked in water described in the step (1) and adopts running water and distilled water successively to soak in regular turn.
5, the bionics method for preparation of precious metal simple substance nanometer material according to claim 1 is characterized in that washing described in step (3) and the step (4), adopts deionized water, acetone and absolute ethyl alcohol alternately to clean 2-6 time.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049226A (en) * | 2010-11-16 | 2011-05-11 | 中国烟草总公司郑州烟草研究院 | Method for preparing TMV template-based nano-gold material |
| CN116715221A (en) * | 2023-06-27 | 2023-09-08 | 内江师范学院 | Biomass-derived porous carbon material and preparation method and application thereof |
-
2007
- 2007-06-28 CN CN 200710042925 patent/CN101081435A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049226A (en) * | 2010-11-16 | 2011-05-11 | 中国烟草总公司郑州烟草研究院 | Method for preparing TMV template-based nano-gold material |
| CN102049226B (en) * | 2010-11-16 | 2013-05-08 | 中国烟草总公司郑州烟草研究院 | Method for preparing TMV template-based nano-gold material |
| CN116715221A (en) * | 2023-06-27 | 2023-09-08 | 内江师范学院 | Biomass-derived porous carbon material and preparation method and application thereof |
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Open date: 20071205 |