CN101077528A - Process for manufactruing superfine nano noble metal solution - Google Patents
Process for manufactruing superfine nano noble metal solution Download PDFInfo
- Publication number
- CN101077528A CN101077528A CN 200610080990 CN200610080990A CN101077528A CN 101077528 A CN101077528 A CN 101077528A CN 200610080990 CN200610080990 CN 200610080990 CN 200610080990 A CN200610080990 A CN 200610080990A CN 101077528 A CN101077528 A CN 101077528A
- Authority
- CN
- China
- Prior art keywords
- precious metal
- solution
- manufacture method
- superfine nano
- acid
- 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.)
- Pending
Links
Abstract
The process of preparing nanometer noble metal solution is one chemical reduction process to reduce Cu, Ag or Au ion stabilized with different dispersant into nanometer Cu, Ag or Au particle while adding various kinds of protecting agent to inhibit the agglutination of nanometer particle. The process can prepare superfine nanometer noble metal solution of average granularity smaller than 5 nm and with high stability and greatly raised tolerance to acid, alkali, oxygen, light and heat, and the superfine nanometer noble metal solution has altered physical characteristic and expanded application range.
Description
Technical field
The present invention relates to a kind of manufacture method of superfine nano precious metal solution; specifically refer in preparation process, add various protective agents and suppress the aggegation of nanometer copper, silver, gold particle, thereby prepare the method for average grain diameter less than precious metal solution such as the superfine nano copper of 5nm, silver, gold.
Background technology
The nanometer technology of preparing is nothing more than physical method and chemical method at present, and its good and bad some comparative descriptions is as follows:
(1) physical method, it includes:
A. vacuum condensation method: be to utilize methods such as vacuum evaporation, heating, high-frequency induction to make particle bodies such as material gasification or formation, quenching then.
Characteristics: purity height, good, the controllable granularity of crystalline structure, but technology and equipment require height.
B. physical crushing method: it is to obtain nano particle by methods such as mechanical crushing, electric spark blasts.
Characteristics: simple to operate, cost is low, but product purity is low, and distribution of particles is inhomogeneous.
C. mechanical ball milling method: be the employing ball grinding method, control the nano particle that suitable condition obtains pure element, alloy or composite.
Characteristics: simple to operate, cost is low, but product purity is low, and distribution of particles is inhomogeneous.
(2) chemical method, it includes:
A. vapour deposition process: the chemical reaction nano materials of utilizing the metallic compound steam.
Characteristics: product purity height, narrow particle size distribution.
B. the precipitation method: precipitating reagent is joined in the salting liquid after the reaction, precipitation heat is handled obtaining nano material.
Characteristics: simple, but purity is low, and particle radius is big, is fit to the preparation nano-oxide.
C. hydrothermal synthesis method: synthetic in fluids such as the aqueous solution or steam under HTHP, again through separating and heat treatment gets nano particle.
Characteristics: the purity height, good dispersion, granularity are easy to control.
D. sol-gal process: through solution, colloidal sol, gel and solidify, generate nano particle through Low Temperature Heat Treatment again with metallic compound.
Characteristics: reaction species is many, product particle homogeneous, and process is easy to control, is fit to the preparation of oxide and II～VI compounds of group.
E. microemulsion method: two kinds of immiscible solvents form emulsion under the effect of surfactant, in microvesicle after nucleation, coalescent, reunion, heat treatment nano particle.
Characteristics: the single dispersion and the interface property of particle are good, and how II～VI family semi-conductor nano particles prepares with this method.
F. chemical reduction method: deliquescent metallic salt is mixed with high molecular polymer or emulsifying agent etc., be prepared into stable dispersion solution after, again with of the metal ion reduction of various reducing agents, obtain the metal nanoparticle of zeroth order with positively charged.
Characteristics: simple to operate, particle disperses to distribute with particle diameter, is suitable for metal (as copper, silver, gold etc.) the nano particle preparation of high oxidation potential.
Above-mentioned utilize in the operation that chemical reduction method prepares various metal nanoparticles no doubt simple; just synthetic nano particle diameter size also can utilize method control nucleation rate such as the kind, concentration, interpolation speed of reducing agent to adjust; but the time through long-time the preservation; these finally reach the stability of specified particle diameter scope than the also aggegation gradually of nanoparticle of small particle diameter.
The present invention then takes the multiple protective mode to increase the aggegation obstacle of nanoparticle, suppresses aggegation simultaneously and takes place, and prepare and can keep the little and stable good nanoparticle of particle diameter, thereby some physical characteristic of change nanoparticle enlarges its range of application.
Summary of the invention
The present invention is to the effect that when carrying out traditional chemical reduction method for preparing nanometer metallic solution, mix one or more water soluble organic substances, as: urea and derivative thereof (as: thiocarbamide, allophanamide etc.), guanidinesalt (as: guanidine nitrate, guanidine sulfate, guanidine hydrochloride, phosphoguanidine etc.); Unsaturated organic acid and its esters are as acrylic acid, methacrylic acid, maleic acid and oleic acid etc.; Organic quaternary ammonium salt is as trimethyl octadecyl ammonium chloride, cacodyl oxide base dodecyl ammonium; Inorganic sulfur nitrogen compound and its esters are as thiosulfuric acid, sulfamic acid, various substituted-amino two bamic acids; Polyacid and its esters are as oxalic acid, citric acid, 1-hydroxy ethylene two see acid (HEDP), amino trimethylene methyl acid phosphate (ATMP), triacetamide etc.; Inorganic salts as: borate, phosphate, pyrophosphate, polyphosphate, bromide, iodide etc. are as disperseing protective agent.
Or after making golden yellow Nano silver solution by conventional method, add suitable oxidant in solution, described oxidant comprises hydrogen peroxide, chlorite, hypochlorite, persulfate, potassium hydrogen persulfate, periodates, iodine or teriodide, bromine or bromate.Change outward appearance, particle diameter, character of the nano metal that forms or the like thus.
Find before reduction reaction, to add an amount of dissolved organic matter in the experiment, can and precious metal ion between chelation takes place, when carrying out reduction reaction, can help to separate nano particle, can prevent the aggegation of nano particle, and form the littler nano particle of particle diameter.
Before reduction reaction, add suitable dissolubility organic or inorganic salt protective agent, also can be in the peripheral ionosphere that forms of metal ion, the agglutination phenomenon when helping to suppress reduction reaction formation nano particle takes place.
And after forming general precious metal nano particle, add an amount of oxidant, then can change the charged situation of precious metal nano particle, and then the surface " plasma effect " (plasma effect) of change nano particle, except show with original diverse color outward appearance, the stability of light, heat, air and soda acid also so is to some extent promoted.
Because the precious metal nano particle has very multiple application in different fields, but it is often limited because of some characteristic, for example Nano Silver has the effect that is showing very much for antibacterial and mouldproof, but, be not suitable for processing light fabric or leather and fur products because Nano Silver itself has yellowish-brown partially tone; Moreover Nano Silver has the color burn phenomenon under the irradiation condition, then is subjected to xanthochromia problem at sunshine on fabric or leather and fur products, and therefore the application for textile or leather and fur products just enjoys restriction.
Various light color in this patent are applied to remove and can solve above-mentioned shades of colour problem in the antibacterial and mouldproof processing of textile or leather and fur products to colourless Nano silver solution, also have excellent fast light, heat-resistant quality, and keep original antibacterial and antimildew function.
The implementation method step that the present invention makes the nanometer precious metal is as follows:
Step 1, preparation dispersant solution:
Dispersant is dissolved in water or the alcohols solvent, the effect of dispersant is to form the stable chelated effect with precious metal ion, be reduced into the atomic time at precious metal ion, form the stabilized nanoscale precious metal solution of particle diameter between 1～100nm by this chelation; And the lasting aggegation of supression precious metal atom, avoid forming the excessive particulate of particle diameter, because of the gravity effect precipitates.The concentration range of general preparation dispersant is 0.1wt% to 10wt%.
Employed in the present invention dispersant comprises various water, pure deliquescent natural polymer, for example: gelatin, hyaluronic acid, collagen hydrolysate etc., or synthetic high polymer, as cellulose derivative: methylcellulose (CMC), hydroxyethylcellulose (HEC), hydroxypropyl cellulose (HPC) etc.; High-molecular copolymer or derivative: maleic anhydride-styrene copolymers macromolecule, polyacrylic acid macromolecule, polyacrylamide, polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) etc.
Dispersant in the superfine nano precious metal solution by weight, is 0.5 to 100 times of precious metal content, and optimum dose is 5 to 50 times of precious metal content.
Step 2, with water or pure dissolubility precious metal salt as: chloroplatinic acid, chlorauride, silver nitrate, silver acetate, copper sulphate, copper nitrate, Schweinfurt green etc. are dissolved in respectively in the water or alcohol solution of above-mentioned dispersant, and form stable precious metal dispersion soln.
Step 3, the aforementioned dispersion protective agent of adding.By this dispersant protective agent, extremely strong chelation power is arranged between solution and precious metal ion, and when metal is ionic state because of the electric charge effect of repelling each other is arranged, ion and interionic are easy to reach the maximum dispersion state.
Disperse the protective agent consumption, by weight, be 0.01 to 100 times of precious metal content, optimum dose is 0.1 to 10 times of precious metal content.
But; once carry out reduction; metal becomes uncharged atomic time; cohesive force between the metal particle of atomic size is very big; be enough to overcome and dispersant between chelation power, metal particle can continuous aggegation be grown up, and the two reaches balance up to chelation power and cohesive force, so with electronation manufactured nanoparticle; its size, and the chelating ability power between dispersant and metal power has absolute relation.
At present general commonly used and best results dispersant-polyvinylpyrrolidone (PVP), chelating ability and cohesive force reach balance when particle diameter grows to 25～50nm greatly.Therefore to make the littler nano metal particles of particle diameter, must break through from two directions:
(i) the tangible chelating section of design on dispersant molecule makes nanoparticle be difficult for being stabilized the chelating district from one and shifts to another chelating district, increases the aggegation obstacle.
(ii) in the ionic state solution that is not reduced as yet, add the due care agent,,, make it produce charge repulsion naturally, avoid excessive aggegation to take place as on nanoparticle, adding or the reserve part electric charge to reduce the agglutination between nanoparticle.The dispersion protective agent that this patent uses promptly is to utilize above-mentioned principle, the agglutination of manufacturing district after increase obstacle, suppressing to reduce between metal ion.
Step 4, add reducing agent at last, positively charged metal ion is reduced into electroneutral atomic state.The present invention is the widely used in the literature diamine of employing, borohydride sodium, tool aldehyde, candy, alcohols structural compounds, as: formaldehyde, citric acid, glucose, vitamin C, inorganic acid or salt as: hypophosphorous acid, sodium thiosulfate, sodium sulphite, nitrite natrium, oxalic acid, other is as reducing agents such as sulfur dioxide, sulfide, bromide, iodide.
Also can comprise the steps five, or replace step 3 with following step 5:
Step 5, can add the oxidation-reduction potential that nano-solution is adjusted in the suitable oxidizing agent, change the charged situation of nanoparticle, change its outward appearance or other physical characteristic.The oxidant consumption by weight, is 0.01 to 100 times of precious metal content, and optimum dose is 0.1 to 10 times of precious metal content.Also comprise by controlling oxidation-reduction potential, for example control terminal point oxidizing potential value at 0 ± 100mV to obtain the technology of different outward appearances or characteristic.
The specific embodiment
Following examples are the manufacture method of various silver-colored nano-solutions:
Embodiment one:
1～100 gram polyvinylpyrrolidone (PVP) is dissolved in 500～900 ml distilled waters, be heated to Celsius 50～100 ℃ be stirred to fully dissolving after, 0.1～40 gram silver nitrate is added in the polyvinylpyrrolidonesolution solution, stir the stable silver ion-PVP dispersion soln of formation after 0～600 minute, at 10～70 ℃ Celsius, the vitamin C aqueous solution with 0.1～500 milliliter of 0.1～100wt% under the vigorous stirring slowly adds, stir about forms the Nano silver solution of golden transparent after 0～600 minute, the triiodide sodium water solution of 1～100 milliliter of 0.1～20wt% is dropped in silver ion-PVP dispersion soln, stir about after 0～600 minute to being close to the water white superfine nano silver aqueous solution.
Embodiment two:
As embodiment one, after generating golden yellow Nano silver solution, add oxidants such as 0.1%～100% hydrogen peroxide, chlorite, hypochlorite, persulfate, potassium hydrogen persulfate, periodates, iodine solution or bromine water respectively and replace the triiodide sodium water solution, and control terminal point oxidizing potential value can obtain near water white Nano silver solution at 0 ± 100mV.
Embodiment three:
1～100 gram polyvinyl alcohol (PVA) is dissolved in 500～900 ml distilled waters, be heated to Celsius 50～100 ℃ be stirred to fully dissolving after, 0.1～40 gram silver nitrate is added in this poly-vinyl alcohol solution, stir the stable silver ion-PVA dispersion soln of formation after 0～600 minute, at 10～70 ℃ Celsius, sodium tetraborate (borax) aqueous solution with 0.1～500 milliliter of 0.1～100wt% under the vigorous stirring slowly adds, behind the stir about 0～600 minute, the borohydride sodium aqueous solution of 1～100 milliliter of 0.1～10wt% is dropped in silver ion-PVA dispersion soln, and stir about must be close to the water white superfine nano silver aqueous solution after 0～600 minute.
Embodiment four:
As embodiment three, but with other water or pure deliquescent natural polymer as gelatin, hyaluronic acid, collagen hydrolysate or synthetic high polymer cellulose derivative: methylcellulose (CMC), hydroxyethylcellulose (HEC) or hydroxypropyl cellulose (HPC); High-molecular copolymer or derivative as: maleic anhydride-styrene copolymers macromolecule, polyacrylic acid macromolecule, polyacrylamide or polyvinylpyrrolidone (PVP) wait replacing for polyvinyl alcohol (PVA), obtain various superfine nanos silver solution.
Embodiment five:
As embodiment three to embodiment four, but with methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, alkyl glycol ether derivant (R
1O (CH
2CH
2O)
nR
2: R
1=C
2～C
6R
2=H, COCH
3N=1～4), polyethylene glycol (molecular weight 200 to 4000), alkyl polyglycol ether (RO (EO)
nH:R=C
8～C
18N=1～100), alkyl phenol polyglycol ether (ArO (EO)
nH:Ar=p-C
8H
17C
6H
4, p-C
9H
19C
6H
4N=1～100), ethylene oxide/propylene oxide copolymer (HO (CH
2CH
2O)
a(CHCH
3CH
2O)
b(CH
2CH
2O)
cH: molecular weight=1100～20000; B 〉=15), propane diols, glycerine wait and replace distilled water, obtains various superfine nanos silver solution.
Embodiment six:
As embodiment three to embodiment five, but with the urea or derivatives thereof as thiocarbamide, allophanamide etc.; Guanidinesalt is as guanidine nitrate, guanidine sulfate, guanidine hydrochloride, phosphoguanidine, guanidine carbonate etc.; Unsaturated organic acid and its esters are as acrylic acid, methacrylic acid, maleic acid and oleic acid etc.; Organic quaternary ammonium salt is as trimethyl octadecyl ammonium chloride, cacodyl oxide base dodecyl ammonium; Inorganic sulfur nitrogen compound and its esters are as thiosulfuric acid, sulfamic acid, various substituted-amino two bamic acids; Polyacid and its esters are as oxalic acid, citric acid, 1-hydroxy ethylene two see acid (HEDP), amino trimethylene methyl see acid (ATMP), triacetamide etc.; Inorganic acid and its esters are as boric acid, phosphoric acid; Polyphosphate is as sodium pyrophosphate, sodium phosphate trimer, sodium trimetaphosphate; Bromide is as ammonium bromide, sodium bromide, KBr; Iodide as: ammonium iodide, sodium iodide, KI wait and replace sodium tetraborate decahydrate, obtain various superfine nanos silver solution.
Embodiment seven:
As embodiment three to embodiment six, but with diamine; Tool aldehyde, candy, alcohols structural compounds, as: formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, citric acid, lemon sodium, glucose, vitamin C etc.; Inorganic acid or salt as: hypophosphorous acid, sodium thiosulfate, sodium sulfite, natrium nitrosum, oxalic acid, sodium oxalate and other inorganic matter as: sulfur dioxide, vulcanized sodium, KBr, KI wait and replace borohydride sodium, obtain various superfine nanos silver solution.
Embodiment eight:
As embodiment one to embodiment seven, but with other silver salt as silver acetate; Various dissolubility mantoquitas are as copper sulphate, Schweinfurt green, copper chloride etc.; Gold salt is as chlorauride; Platinum salt replaces silver nitrate as: chloroplatinic acid etc., disperses, protects, reduces behind the supervisor, obtains various superfine nano precious metal solution.
Embodiment nine:
1～100 gram polyvinylpyrrolidone (PVP) is dissolved in 500～900 ml distilled waters, be heated to Celsius 50～100 ℃ be stirred to fully dissolving after, 0.1～40 gram silver nitrate is added in the polyvinylpyrrolidonesolution solution, stir the stable silver ion-PVP dispersion soln of formation after 0～600 minute (ORP=450 ± 100mV), at 10～70 ℃ Celsius, sodium thiosulfate solution with 0.1～500 milliliter of 0.1～100wt% under the vigorous stirring slowly adds, stir about is (ORP=0 ± 100mV), obtain being close to the water white superfine nano silver aqueous solution after 0～600 minute.
Embodiment ten:
As nine, with other water or pure deliquescent natural polymer as: gelatin, hyaluronic acid, collagen hydrolysate or synthetic high polymer are as cellulose derivative: methylcellulose (CMC), hydroxyethylcellulose (HEC), hydroxypropyl cellulose (HPC); High-molecular copolymer or derivative as: maleic anhydride-styrene copolymers macromolecule, polyacrylic acid macromolecule, polyacrylamide, polyvinyl alcohol (PVA) wait and replace polyvinylpyrrolidone (PVP), obtain various superfine nanos silver solution.
Embodiment 11:
As embodiment nine to embodiment ten, with methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, alkyl glycol ether derivant (R
1O (CH
2CH
2O)
nR
2: R
1=C
2～C
6R
2=H, COCH
3N=1～4), polyethylene glycol (molecular weight 200 to 4000), alkyl polyglycol ether (RO (EO)
nH:R=C
8～C
18N=1～100), alkyl phenol polyglycol ether (ArO (EO)
nH:Ar=p-C
8H
17C
6H
4, p-C
9H
19C
6H
4N=1～100), ethylene oxide/propylene oxide copolymer (HO (CH
2CH
2O)
a(CHCH
3CH
2O)
b(CH
2CH
2O)
cH: molecular weight=1100～20000; B 〉=15), propane diols, glycerine wait and replace distilled water, obtains various superfine nanos silver solution.
Embodiment 12:
As embodiment nine to embodiment 11, with diamine, borohydride sodium; Tool aldehyde, candy, alcohols structural compounds, as: formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, citric acid, lemon sodium, glucose, vitamin C etc.; Inorganic acid or salt as: hypophosphorous acid, sodium sulfite, natrium nitrosum, oxalic acid, sodium oxalate and other inorganic matter as: sulfur dioxide, vulcanized sodium, KBr, KI wait and replace sodium thiosulfate, obtain various superfine nanos silver solution.
Embodiment 13:
As embodiment nine to embodiment 12, with other silver salt as silver acetate; Various dissolubility mantoquitas are as copper sulphate, Schweinfurt green, copper chloride etc.; The gold salt as: chlorauride); Platinum salt replaces silver nitrate as: chloroplatinic acid etc., disperses, protects, reduces behind the supervisor, obtains various superfine nano precious metal solution.
More than first to implementing 13 examples, described colourless superfine nano silver solution is applied to fabric or leather treatment, to obtain antibacterial and bactericidal fabric of tool or leather; Make an addition to coating, to obtain the antibacterial and bactericidal effect of tool.Wherein use avirulent reagent as conditions such as silver acetate, vitamin C, citric acid, guanidine hydrochloride and inorganic iodides, the superfine nano that is obtained silver solution can be used in food or the medical treatment, can obtain that tool is antibacterial, anticorrosion, effects such as sterilization and treatment.
Through detecting, can reach following result at the above various superfine nano precious metal solution that manufacture.
1. the measure analysis of nanoscale:
According to transmission electron microscope test general rule JY/T011-1966, use Hitachi H-7100 transmission electron microscope, electron accelerating voltage is 80-100KV, and resolution ratio is 0.34nm, the particle size and the distribution scenario of test implementation example one superfine nano silver solution.The result of observation superfine nano silver solution example after depositing 120 days shows particle diameter less than 30nm, and the particle diameter of maximum distribution (35.7～47.7%) is distributed in 15nm.The particle size and the distribution scenario of the superfine nano silver solution of test implementation example three to embodiment 13.The result of the superfine nano silver solution example of observation after depositing 120 days shows that particle diameter is less than 5nm.
2. antibacterial and mouldproof test:
After the concentration of the superfine nano silver solution that embodiment one to embodiment 13 is synthesized is adjusted to 10ppm to 100ppm, entrust Taiwan Test Technology Co., Ltd., standard method of test according to U.S.Pharmacopeia 26NF 21Microbiological Test (51), be 3 hours and 24 hours action time, and the detection strain name is staphylococcus aureus, pneumobacillus, Escherichia coli, Pseudomonas aeruginosa and drug resistance staphylococcus aureus.Result of the test: all do not detect these bacteriums in above-mentioned condition, antibacterial in other words value＞99.999% shows that superfine nano silver solution of the present invention is to above-mentioned bacterial strains tool obvious sterilization effect.
3. light fastness test:
After the concentration of the superfine nano silver solution that embodiment one to embodiment 13 is synthesized is adjusted to 100ppm, use the impregnation mode to be machined in the cotton flat fabric of handling through fluorescent brightening, again after 150～170 ℃ * 30～45sec heat baking typing Celsius, with the UV-irradiation of medium pressure mercury lamp wave-length coverage 365 ± 50nm, the cumulative exposure energy is 300mj/cm
2Result of the test:, do not have obvious aberration with not irradiating ultraviolet light cloth specimen contrast.
4. heat-resistance test:
After the concentration of the superfine nano silver solution that embodiment one to embodiment five is synthesized is adjusted to 100ppm, use the impregnation mode to be machined in the cotton flat fabric of handling through fluorescent brightening, after 150～170 ℃ * 30～45sec heat baking typing Celsius, adopt 80 ℃ * 8hr Celsius with hot-air oven and handle again.Result of the test: with handle the cloth specimen contrast without hot-air oven, do not have obvious aberration.
Claims (11)
1. the manufacture method of a superfine nano precious metal solution is characterized in that, this manufacture method is:
Step 1, preparation concentration range are the dispersant solution of 0.1wt% to 10wt%, and this dispersant is dissolved in water or the alcohols equal solvent;
Step 2, water or pure dissolubility precious metal salt are dissolved in the water or alcohol solution of above-mentioned dispersant, and form stable precious metal dispersion soln;
Step 3, adding disperse protective agent;
Step 4, adding reducing agent are reduced into electroneutral atomic state with positively charged metal ion;
Also can comprise the steps, or replace step 3 with following step:
The oxidation-reduction potential of nano-solution is adjusted in step 5, the agent of adding suitable oxidizing, changes the charged situation of nanoparticle, changes its outward appearance and other physical characteristic.
2. the manufacture method of superfine nano precious metal solution as claimed in claim 1, it is characterized in that, dispersant in the superfine nano precious metal solution, by weight, be 0.5 to 100 times of precious metal content, optimum dose is 5 to 50 times of precious metal content.
3. the manufacture method of superfine nano precious metal solution as claimed in claim 1 is characterized in that, dispersion solvent comprises water or alcohols as methyl alcohol, ethanol, isopropyl alcohol; Ethylene glycol and derivative thereof are as alkyl glycol ether derivant (R
1O (CH
2CH
2O)
nR
2: R
1=C
2～C
6R
2=H, COCH
3N=1～4), polyethylene glycol (molecular weight 200 to 4000) and derivative thereof are as alkyl polyglycol ether (RO (EO)
nH:R=C
8～C
18N=1～100), alkyl phenol polyglycol ether (ArO (EO)
nH:Ar=p-C
8H
17C
6H
4, p-C
9H
19C
6H
4N=1～100), ethylene oxide/propylene oxide copolymer (HO (CH
2CH
2O)
a(CHCH
3CH
2O)
b(CH
2CH
2O)
cH: molecular weight=1100～20000; B 〉=15); Other polyalcohol is as propane diols, glycerine, D-sorbite, xylitol etc.
4. the manufacture method of superfine nano precious metal solution as claimed in claim 1 is characterized in that, dispersant comprises various water, deliquescent natural, the synthetic high polymer of alcohol, comprises: cellulose derivative, high-molecular copolymer or derivative.
5. the manufacture method of superfine nano precious metal solution as claimed in claim 1 is characterized in that, disperses the protective agent consumption, by weight, is 0.01 to 100 times of precious metal content, and optimum dose is 0.1 to 10 times of precious metal content.
6. the manufacture method of superfine nano precious metal solution as claimed in claim 1; it is characterized in that, disperse protective agent to comprise urea and derivative, guanidinesalt, unsaturated organic acid or its esters, various organic quaternary ammonium salt, inorganic sulfur nitrogen compound, polyacid, inorganic salts etc.
7. the manufacture method of superfine nano precious metal solution as claimed in claim 1, it is characterized in that, when using reducing process to prepare superfine nano precious metal solution, the reducing agent consumption, by weight, be 0.01 to 100 times of precious metal content, optimum dose is 0.1 to 10 times of precious metal content.
8. the manufacture method of superfine nano precious metal solution as claimed in claim 1 is characterized in that reducing agent comprises diamine, borohydride sodium; Tool aldehyde, candy, alcohols structural compounds, as: formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, citric acid, lemon sodium, glucose, vitamin C etc.; Inorganic acid is as: hypophosphorous acid, sulfurous acid, nitrous acid, thiosulfuric acid, oxalic acid, and hydrogen sulfide, sulfur dioxide, sulfide, bromide, iodide etc.
9. the manufacture method of superfine nano precious metal solution as claimed in claim 1 is characterized in that, when using oxidizing process to prepare colourless Nano silver solution, the oxidant consumption, by weight, be 0.01 to 100 times of precious metal content, optimum dose is 0.1 to 10 times of precious metal content.
10. the manufacture method of superfine nano precious metal solution as claimed in claim 1, it is characterized in that oxidant comprises the oxidants such as various solution of hydrogen peroxide, chlorite, hypochlorite, persulfate, potassium hydrogen persulfate, periodates, iodine, teriodide or bromine.
11. the manufacture method of superfine nano precious metal solution as claimed in claim 1 is characterized in that, comprises by the control oxidation-reduction potential to obtain the technology of different outward appearances or characteristic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610080990 CN101077528A (en) | 2006-05-26 | 2006-05-26 | Process for manufactruing superfine nano noble metal solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610080990 CN101077528A (en) | 2006-05-26 | 2006-05-26 | Process for manufactruing superfine nano noble metal solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101077528A true CN101077528A (en) | 2007-11-28 |
Family
ID=38905285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610080990 Pending CN101077528A (en) | 2006-05-26 | 2006-05-26 | Process for manufactruing superfine nano noble metal solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101077528A (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829413A (en) * | 2010-05-06 | 2010-09-15 | 上海大胜卫生用品制造有限公司 | Sterilizing and anti-virus type mask |
| CN101869988A (en) * | 2010-05-06 | 2010-10-27 | 复旦大学 | Method for preparing water base nano silver |
| CN101869989A (en) * | 2010-06-03 | 2010-10-27 | 中国林业科学研究院林产化学工业研究所 | Method for preparing water dispersible metal nano-particles |
| CN101956027A (en) * | 2010-10-13 | 2011-01-26 | 四川大学 | Sheep fur with nanometer antibacterial function and preparation method thereof |
| CN102218542A (en) * | 2011-05-12 | 2011-10-19 | 陕西科技大学 | Nanogold preparation method |
| CN101875131B (en) * | 2009-12-15 | 2012-07-04 | 武汉大学 | Preparation method of platinum nanoparticles |
| CN102873335A (en) * | 2011-07-14 | 2013-01-16 | 东南大学 | Preparation method of temperature-sensitive water-soluble silver nanoparticles |
| CN102929066A (en) * | 2012-11-14 | 2013-02-13 | 京东方科技集团股份有限公司 | Electrophoresis buffer and preparation method of electrophoresis solution, electrophoresis microcapsule and electrophoresis device |
| CN102120265B (en) * | 2010-01-07 | 2013-04-10 | 中国科学院化学研究所 | Preparation method of colloid of mono-dispersed silver nano particles and nano silver powder and conductive ink thereof |
| CN103217847A (en) * | 2012-01-18 | 2013-07-24 | 广州奥翼电子科技有限公司 | Electrophoresis display particle comprising metal component and preparation method as well as functions thereof |
| WO2013117101A1 (en) * | 2012-02-06 | 2013-08-15 | 京东方科技集团股份有限公司 | Electrophoretic particle, preparation method thereof and electrophoretic microcapsule |
| CN103658672A (en) * | 2012-09-11 | 2014-03-26 | 中国科学院大连化学物理研究所 | Aqueous phase preparation method for metal nanoparticles |
| CN104325151A (en) * | 2014-10-11 | 2015-02-04 | 中国振华集团云科电子有限公司 | Silver powder preparing method |
| CN105127413A (en) * | 2015-09-18 | 2015-12-09 | 温州大学 | Precious metal nanoring and preparation method thereof |
| CN105562715A (en) * | 2016-03-11 | 2016-05-11 | 吉林大学 | Low-temperature water-phase preparation method for porous gold nanocrystals |
| CN108372311A (en) * | 2018-03-21 | 2018-08-07 | 北京科技大学 | A method of preparing copper nano-particle using modification of polysaccharides |
| CN108705100A (en) * | 2018-06-07 | 2018-10-26 | 蒋建华 | A kind of preparation method of nanometer of platinum particles |
| CN109545696A (en) * | 2018-11-28 | 2019-03-29 | 哈尔滨工业大学 | A method of law temperature joining high-temperature service connector is prepared using single phase nano yellow gold soldering paste |
| CN109940169A (en) * | 2019-04-19 | 2019-06-28 | 陕西科技大学 | A kind of Nanometer Copper and preparation method thereof |
| CN110142416A (en) * | 2019-01-21 | 2019-08-20 | 水利部南京水利水文自动化研究所 | A kind of method that dried orange peel extracting solution prepares nano-Ag particles |
| CN111992734A (en) * | 2020-08-21 | 2020-11-27 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
| CN112264628A (en) * | 2020-10-28 | 2021-01-26 | 中国工程物理研究院激光聚变研究中心 | Preparation method of gold aerogel |
| CN115194171A (en) * | 2022-05-27 | 2022-10-18 | 氢电中科（广州）新能源设备有限公司 | Highly-dispersed platinum nanoparticle solution and preparation method thereof |
-
2006
- 2006-05-26 CN CN 200610080990 patent/CN101077528A/en active Pending
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875131B (en) * | 2009-12-15 | 2012-07-04 | 武汉大学 | Preparation method of platinum nanoparticles |
| CN102120265B (en) * | 2010-01-07 | 2013-04-10 | 中国科学院化学研究所 | Preparation method of colloid of mono-dispersed silver nano particles and nano silver powder and conductive ink thereof |
| CN101829413B (en) * | 2010-05-06 | 2012-07-04 | 上海大胜卫生用品制造有限公司 | Sterilizing and anti-virus type mask |
| CN101829413A (en) * | 2010-05-06 | 2010-09-15 | 上海大胜卫生用品制造有限公司 | Sterilizing and anti-virus type mask |
| CN101869988A (en) * | 2010-05-06 | 2010-10-27 | 复旦大学 | Method for preparing water base nano silver |
| CN101869989A (en) * | 2010-06-03 | 2010-10-27 | 中国林业科学研究院林产化学工业研究所 | Method for preparing water dispersible metal nano-particles |
| CN101956027A (en) * | 2010-10-13 | 2011-01-26 | 四川大学 | Sheep fur with nanometer antibacterial function and preparation method thereof |
| CN101956027B (en) * | 2010-10-13 | 2013-06-05 | 四川大学 | Sheep fur with nanometer antibacterial function and preparation method thereof |
| CN102218542A (en) * | 2011-05-12 | 2011-10-19 | 陕西科技大学 | Nanogold preparation method |
| CN102218542B (en) * | 2011-05-12 | 2013-04-10 | 陕西科技大学 | Nanogold preparation method |
| CN102873335A (en) * | 2011-07-14 | 2013-01-16 | 东南大学 | Preparation method of temperature-sensitive water-soluble silver nanoparticles |
| CN103217847A (en) * | 2012-01-18 | 2013-07-24 | 广州奥翼电子科技有限公司 | Electrophoresis display particle comprising metal component and preparation method as well as functions thereof |
| WO2013117101A1 (en) * | 2012-02-06 | 2013-08-15 | 京东方科技集团股份有限公司 | Electrophoretic particle, preparation method thereof and electrophoretic microcapsule |
| CN103658672B (en) * | 2012-09-11 | 2015-10-21 | 中国科学院大连化学物理研究所 | A kind of aqueous phase preparation method of metal nanoparticle |
| CN103658672A (en) * | 2012-09-11 | 2014-03-26 | 中国科学院大连化学物理研究所 | Aqueous phase preparation method for metal nanoparticles |
| CN102929066A (en) * | 2012-11-14 | 2013-02-13 | 京东方科技集团股份有限公司 | Electrophoresis buffer and preparation method of electrophoresis solution, electrophoresis microcapsule and electrophoresis device |
| CN104325151A (en) * | 2014-10-11 | 2015-02-04 | 中国振华集团云科电子有限公司 | Silver powder preparing method |
| CN105127413A (en) * | 2015-09-18 | 2015-12-09 | 温州大学 | Precious metal nanoring and preparation method thereof |
| CN105127413B (en) * | 2015-09-18 | 2017-07-21 | 温州大学 | Noble metal nano ring and preparation method thereof |
| CN105562715A (en) * | 2016-03-11 | 2016-05-11 | 吉林大学 | Low-temperature water-phase preparation method for porous gold nanocrystals |
| CN105562715B (en) * | 2016-03-11 | 2017-07-14 | 吉林大学 | A kind of low temperature aqueous phase preparation method of porous gold nanocrystals |
| CN108372311A (en) * | 2018-03-21 | 2018-08-07 | 北京科技大学 | A method of preparing copper nano-particle using modification of polysaccharides |
| CN108372311B (en) * | 2018-03-21 | 2019-07-16 | 北京科技大学 | A method of copper nano-particle is prepared using modification of polysaccharides |
| CN108705100A (en) * | 2018-06-07 | 2018-10-26 | 蒋建华 | A kind of preparation method of nanometer of platinum particles |
| CN109545696A (en) * | 2018-11-28 | 2019-03-29 | 哈尔滨工业大学 | A method of law temperature joining high-temperature service connector is prepared using single phase nano yellow gold soldering paste |
| CN110142416A (en) * | 2019-01-21 | 2019-08-20 | 水利部南京水利水文自动化研究所 | A kind of method that dried orange peel extracting solution prepares nano-Ag particles |
| CN109940169A (en) * | 2019-04-19 | 2019-06-28 | 陕西科技大学 | A kind of Nanometer Copper and preparation method thereof |
| CN109940169B (en) * | 2019-04-19 | 2022-03-29 | 陕西科技大学 | Nano copper and preparation method thereof |
| CN111992734A (en) * | 2020-08-21 | 2020-11-27 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
| CN111992734B (en) * | 2020-08-21 | 2022-02-22 | 山东建邦胶体材料有限公司 | Preparation method of nano-silver with controllable particle size |
| CN112264628A (en) * | 2020-10-28 | 2021-01-26 | 中国工程物理研究院激光聚变研究中心 | Preparation method of gold aerogel |
| CN115194171A (en) * | 2022-05-27 | 2022-10-18 | 氢电中科（广州）新能源设备有限公司 | Highly-dispersed platinum nanoparticle solution and preparation method thereof |
| CN115194171B (en) * | 2022-05-27 | 2023-09-26 | 氢电中科（广州）新能源设备有限公司 | Highly dispersed platinum nanoparticle solution and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101077528A (en) | Process for manufactruing superfine nano noble metal solution | |
| CN1261268C (en) | Nanometer silver sol and preparing method thereof | |
| Abdelgawad et al. | Antimicrobial wound dressing nanofiber mats from multicomponent (chitosan/silver-NPs/polyvinyl alcohol) systems | |
| US9080255B2 (en) | Method of producing silver nanowires in large quantities | |
| CN108372313B (en) | Nano silver wire dispersion liquid with small wire diameter distribution and preparation method of conductive ink thereof | |
| JP6104681B2 (en) | Method for producing high aspect ratio silver nanowires | |
| CN106810800B (en) | A kind of preparation method of antibiotic property polyvinyl alcohol/nanocrystalline cellulose-graphene oxide PVA/CNC-GO composite membrane | |
| EP3141323B1 (en) | Complex, method for producing complex, dispersion, method for producing dispersion, and optical material | |
| JP5479347B2 (en) | Method for forming stabilized metal salt particles | |
| CN110934153B (en) | Zirconium phosphate carrier, zirconium phosphate copper-carrying antibacterial agent, zirconium phosphate antibacterial agent, preparation method and application thereof | |
| CN110051837B (en) | CuO/ZnO/Au nano-particles and preparation method and application thereof | |
| CN1876293A (en) | Nano-class silver colloidal solution and preparation method thereof | |
| CN101050315A (en) | Method for preparing Nano silver grain, and prepared Nano silver grain | |
| CN110144093B (en) | Preparation method of nano-silver/cellulose/polyvinyl alcohol composite film | |
| CN106149460B (en) | High antibiotic property water proof type conductive paper of high intensity and preparation method thereof | |
| JP2016166402A (en) | Method for manufacturing silver nanowire | |
| CN1792508A (en) | Nano silver using inorganic metallic oxide as carrier and preparation process thereof | |
| CN112795098A (en) | Antibacterial plastic and preparation method thereof | |
| TWI337892B (en) | ||
| CN1947520A (en) | Aqueous solution contg. nano-silver dispersing particles and its prepn. method | |
| CN113261566B (en) | Preparation method of basic magnesium hypochlorite loaded metal organic framework bacteriostatic agent | |
| CN111995799B (en) | Preparation method of nano-silver/cellulose composite antibacterial material | |
| CN114015120A (en) | Antibacterial agent for plastic modification based on black phosphorus alkene and preparation method thereof | |
| JP4873396B2 (en) | Metal oxide nanofiber / polysaccharide complex | |
| KR101871963B1 (en) | Antibiotic compound and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |