CN102776565B - Method for preparing nano-structure single crystal silver - Google Patents
Method for preparing nano-structure single crystal silver Download PDFInfo
- Publication number
- CN102776565B CN102776565B CN201210297462.5A CN201210297462A CN102776565B CN 102776565 B CN102776565 B CN 102776565B CN 201210297462 A CN201210297462 A CN 201210297462A CN 102776565 B CN102776565 B CN 102776565B
- Authority
- CN
- China
- Prior art keywords
- silver
- single crystal
- nano
- structure single
- activated carbon
- 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.)
- Expired - Fee Related
Links
Abstract
The invention relates to a method for preparing nano-structure single crystal silver. The method comprises the following steps of: reducing high-conductivity forming porous activated carbon containing chloride ion, putting the activated carbon into a silver-containing precursor solution, growing nano-structure single crystal silver on the surface of the activated carbon, providing a crystal nucleus and slow and stable crystal growth environment required by growth of single crystal silver through the silver-containing precursor and proper chlorine content, and obtaining nano silver single crystal with multiple features by controlling the concentration of the solution containing the silver-containing precursor and the growth time. The method belongs to a green synthesis method, pollution is avoided, any additive is not required, and the nano-structure single crystal silver is grown on the surface of the forming porous activated carbon at room temperature; the nano-structure single crystal silver is high in productivity, high in purity and easily separated from the forming porous activated carbon, the silver is naturally stripped after growth, and the activated carbon is ultrasonically treated by absolute ethyl alcohol or alkaline liquor and can be regenerated; and the obtained single crystal silver has the characteristics of high mechanical strength, high conductivity and low crystal defect.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, especially relate to a kind of preparation method of nano-structure single crystal silver.
Background technology
Silver nano material, especially monocrystalline, because of its excellent conduction, heat transfer property, catalysis and antibiosis specific performance and become current research focus.Nano silver material has broad application prospects in fields such as electronic devices and components, photoconductive fiber, conductive silver paste, chemical/biological sensors, chemical industry catalysis, conductive filler materials.
At present, the preparation method of silver nano material mainly contains: ball milled, template, liquid phase reduction, electrochemical reducing etc.Ball milled can prepare flake silver powder, needs to add more auxiliary agent in mechanical milling process, and this ball-milling medium impurity finally cannot be removed completely, affects the use properties of flake silver powder in electric slurry.Though Template preparation method can obtain the silver nano material of height ratio, need to eliminate template in preparation process, add the complicacy of technique and reduce the output of product, there is certain limitation.In the process of liquid phase reaction method synthesis silver nano material, there is reduction temperature high, easy contaminate environment, complicated process of preparation, the shortcomings such as product purity is not high, the nano silver wire of gained on-monocrystalline, unsuitable utilization and extention.
Through finding the literature search of prior art, in linear chitosan film, in-situ reducing prepares Nano silver grain and silver-colored single crystal, Acta Phys.Chim.Sin., 2003,19 (5): 464-468, this article adopts photoreduction method and electrochemical method has prepared spherical silver nanoparticles in chitosan film and outward appearance silver-colored monocrystalline triangular in shape, hexagonal, and the silver-colored monocrystalline pattern generated is single and productive rate is lower.In the existing work of the present inventor, patent of invention CN102418118A discloses a kind of electrochemistry and assists the method preparing specific form nano-silver powder, be respectively negative electrode, anode with working electrode with to electrode, immerse in the solution of silver ion or colloidal sol, the nano silver powder of different morphologies is prepared by electrochemical reaction, but the nanometer silver preparing gained is not monocrystalline, and in reaction process, silver ions is directly reduced into silver-colored simple substance, does not introduce new crystal seed.
Low cost, in batches, stably preparing Silver Nanostructures monocrystalline, and solve the silver surface pollution problem owing to adopting the organic additives such as reductive agent, template and dispersion agent to cause in preparation process, is difficult point wherein.Nanostructure nano silver material being made morphology controllable, by greatly improving the using value of silver, therefore, still needs to develop a kind of high yield, can obtain the preparation method of the nano silver material of controlled crystallinity and pattern.
Summary of the invention
Object of the present invention is exactly provide the preparation method of a kind of high yield, free of contamination green syt nano-structure single crystal silver to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions;
A preparation method for nano-structure single crystal silver, the method comprises the following steps:
(1) the reducing process of pressed active carbon:
Pressed active carbon be impregnated in massfraction be 5 ~ 20% ammonia soln or dehydrated alcohol in, take out after 10min ~ 2h in 60 ~ 120 DEG C of oven dry, obtain pretreated gac;
(2) Constitutive active carbon surface grows nano-structure single crystal silver:
Preparation argentiferous precursor solution, impregnated in wherein by pretreated gac, grows the nano-structure single crystal silver of different-shape, be product after at room temperature for some time at activated carbon surface.
Described pressed active carbon has good electroconductibility and water-intake rate, and wherein the electric conductivity of gac is 200 ~ 1000S/m, and chloride ion content is 0.01 ~ 1wt%.
Described argentiferous precursor solution is the silver ammino solution of concentration 0.0001 ~ 0.1mol/L.
In step (2), the growth time of nano-structure single crystal silver is 1min ~ 24h.
The structure of described nano-structure single crystal silver is one or more in particulate state, band shape, sheet, spination or threadiness.
The growth mechanism of nano-structure single crystal silver of the present invention is: in the silver ammino solution of argentiferous presoma, silver ammino ion ionization generates silver ions and hydroxide ion, silver ion diffusion reacts to activated carbon surface and surperficial chlorion and generates silver chloride crystal seed, the reduction group on this monocrystalline and active carbon pore structure surface forms galvanic cell by carbon skeleton, obtaining electronics is reduced into as silver-colored monocrystalline, and continue constantly to obtain as positive pole the electronics that active carbon pore structure surface reduction group electrochemical conversion provides, the silver ions of catching in solution causes elemental silver deposition growing thereon, hydroxide ion is enriched in the effect that negative pole plays the regeneration of reductibility functional group.Certain density silver ammino solution presoma, appropriate cl content provide monocrystal silver growth required for nucleus and slowly stable environment of crystal growth.
Compared with prior art, present invention utilizes galvanic principles and the porous carbon pore structure surface reduction functional group of shaping porous activated carbon itself, when without any need for reductive agent, tensio-active agent and external energy, silver-colored simple substance just can constantly be deposited out.The silver-colored monocrystalline controlling to obtain different-shape nano structure by the concentration and growth time regulating argentiferous precursor solution has the following advantages:
1. pollution-free, green synthesis method, does not need to add any additive, can grow Silver Nanostructures monocrystalline at room temperature, at a normal.
2. the pattern of nano-structure single crystal silver is controlled by means of only the concentration of argentiferous precursor solution and growth time, and experimental procedure is simple to operation.
3. the nano-structure single crystal silver productive rate of gained is high, purity is high, is easy to be separated with shaping porous activated carbon, porous charcoal dehydrated alcohol or alkali lye supersound process renewable.
4. the characteristics such as high, the superpower electroconductibility of product tool physical strength, crystal defect be few.
Accompanying drawing explanation
Fig. 1 prepares the scanning electron microscopic picture of the banded nanometer silver monocrystalline obtained for embodiment 2.
Fig. 2 prepares the scanning electron microscopic picture of the flake nano silver monocrystalline obtained for embodiment 4.
Fig. 3 prepares the transmission electron microscope diffraction spot picture of the banded nanometer silver monocrystalline obtained for embodiment 2.
Fig. 4 prepares the transmission electron microscope diffraction spot picture of the flake nano silver monocrystalline obtained for embodiment 4.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail; the present embodiment is implemented under premised on technical solution of the present invention; give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Preparation massfraction is the ammonia soln of 20%, gac is flooded wherein 10min, in 60 DEG C of oven dry after taking-up; Compound concentration is the silver ammino solution of 0.0001mol/L, is placed in one by pretreated gac, at room temperature grows particulate state nano-structure single crystal silver at activated carbon surface after 1min.Wherein the electric conductivity of gac is 200S/m, and chloride ion content is 0.01wt%.
Embodiment 2
Preparation massfraction is the ammonia soln of 5%, gac is flooded wherein 30min, in 80 DEG C of oven dry after taking-up; Compound concentration is the silver ammino solution of 0.005mol/L, pretreated gac is placed in one, at room temperature grow beltlike nanostructures monocrystal silver at activated carbon surface after 1h, as shown in Figure 1, transmission electron microscope diffraction spot picture as shown in Figure 3 for stereoscan photograph.Wherein the electric conductivity of gac is 600S/m, and chloride ion content is 0.05wt%.
Embodiment 3
Preparation massfraction is the ammonia soln of 10%, gac is flooded wherein 1h, in 100 DEG C of oven dry after taking-up; Compound concentration is the silver ammino solution of 0.01mol/L, is placed in one by pretreated gac, at room temperature grows spination nano-structure single crystal silver at activated carbon surface after 40min.Wherein the electric conductivity of gac is 800S/m, and chloride ion content is 0.08wt%.
Embodiment 4
Preparation massfraction is the ammonia soln of 5%, gac is flooded wherein 1h, in 120 DEG C of oven dry after taking-up; Compound concentration is the silver ammino solution of 0.001mol/L, pretreated gac is placed in one, at room temperature grow flake nano structure monocrystal silver at activated carbon surface after 24h, as shown in Figure 2, transmission electron microscope diffraction spot picture as shown in Figure 4 for stereoscan photograph.Wherein the electric conductivity of gac is 600S/m, and chloride ion content is 0.05wt%.
Embodiment 5
Gac is flooded 2h in dehydrated alcohol, in 80 DEG C of oven dry after taking-up; Compound concentration is the silver ammino solution of 0.1mol/L, is placed in one by pretreated gac, at room temperature grows fiber-like nanostructures monocrystal silver at activated carbon surface after 6h.Wherein the electric conductivity of gac is 950S/m, and chloride ion content is 0.975wt%.
Embodiment 6
A preparation method for nano-structure single crystal silver, the method comprises the following steps:
(1) the reducing process of pressed active carbon: pressed active carbon be impregnated in dehydrated alcohol, take out in 60 DEG C of oven dry after 10min, obtain pretreated gac, wherein, pressed active carbon has good electroconductibility and water-intake rate, wherein the electric conductivity of gac is 200S/m, and chloride ion content is 0.01wt%;
(2) Constitutive active carbon surface grows nano-structure single crystal silver: the silver ammino solution of compound concentration 0.0001mol/L, pretreated gac be impregnated in wherein, growing structure at activated carbon surface after at room temperature keeping 24h is granular nanometer structure monocrystal silver, is product.
Embodiment 7
A preparation method for nano-structure single crystal silver, the method comprises the following steps:
(1) the reducing process of pressed active carbon: pressed active carbon be impregnated in dehydrated alcohol, take out in 120 DEG C of oven dry after 2h, obtain pretreated gac, wherein, pressed active carbon has good electroconductibility and water-intake rate, wherein the electric conductivity of gac is 1000S/m, and chloride ion content is 1wt%;
(2) Constitutive active carbon surface grows nano-structure single crystal silver: compound concentration is the silver ammino solution of 0.1mol/L, pretreated gac be impregnated in wherein, grow jagged nano-structure single crystal silver at activated carbon surface after at room temperature keeping 1min, be product.
Claims (4)
1. a preparation method for nano-structure single crystal silver, is characterized in that, the method comprises the following steps:
(1) the reducing process of pressed active carbon:
Pressed active carbon be impregnated in massfraction be 5 ~ 20% ammonia soln or dehydrated alcohol in, take out after 10min ~ 2h in 60 ~ 120 DEG C of oven dry, obtain pretreated gac;
(2) Constitutive active carbon surface grows nano-structure single crystal silver:
Preparation argentiferous precursor solution, impregnated in wherein by pretreated gac, grows the nano-structure single crystal silver of different-shape, be product after at room temperature for some time at activated carbon surface;
Described argentiferous precursor solution is the silver ammino solution of concentration 0.0001 ~ 0.1mol/L.
2. the preparation method of a kind of nano-structure single crystal silver according to claim 1, it is characterized in that, described pressed active carbon has good electroconductibility and water-intake rate, and wherein the electric conductivity of gac is 200 ~ 1000S/m, and chloride ion content is 0.01 ~ 1wt%.
3. the preparation method of a kind of nano-structure single crystal silver according to claim 1, is characterized in that, in step (2), the growth time of nano-structure single crystal silver is 1min ~ 24h.
4. the preparation method of a kind of nano-structure single crystal silver according to claim 1, is characterized in that, the structure of described nano-structure single crystal silver is one or more in particulate state, band shape, sheet, spination or threadiness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210297462.5A CN102776565B (en) | 2012-08-20 | 2012-08-20 | Method for preparing nano-structure single crystal silver |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210297462.5A CN102776565B (en) | 2012-08-20 | 2012-08-20 | Method for preparing nano-structure single crystal silver |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102776565A CN102776565A (en) | 2012-11-14 |
| CN102776565B true CN102776565B (en) | 2015-05-20 |
Family
ID=47121664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210297462.5A Expired - Fee Related CN102776565B (en) | 2012-08-20 | 2012-08-20 | Method for preparing nano-structure single crystal silver |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102776565B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103521777A (en) * | 2013-10-11 | 2014-01-22 | 南京邮电大学 | Method for preparing two-dimensional silver nanosheets of different shapes |
| CN106031950A (en) * | 2015-11-10 | 2016-10-19 | 南京工业大学 | Rapid and efficient ultrafine silver nanowire preparation method |
| CN107978765B (en) * | 2017-12-29 | 2021-02-02 | 中南大学 | Method for manufacturing supported nano silver catalyst and composite air electrode |
| CN113445075A (en) * | 2021-06-07 | 2021-09-28 | 湖南科技学院 | Method for preparing metal single crystal by electrochemical deposition of solid precursor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251326A (en) * | 1999-10-20 | 2000-04-26 | 中山大学 | Method for making nanometer noble metal microparticles |
| CN101708884A (en) * | 2009-11-06 | 2010-05-19 | 哈尔滨工业大学深圳研究生院 | Method for removing bromate in water by silver coated activated carbon |
-
2012
- 2012-08-20 CN CN201210297462.5A patent/CN102776565B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251326A (en) * | 1999-10-20 | 2000-04-26 | 中山大学 | Method for making nanometer noble metal microparticles |
| CN101708884A (en) * | 2009-11-06 | 2010-05-19 | 哈尔滨工业大学深圳研究生院 | Method for removing bromate in water by silver coated activated carbon |
Non-Patent Citations (2)
| Title |
|---|
| 赖奕坚.成型活性炭的银离子吸附研究.《中国优秀硕士论文全文数据库(工程科技I辑)》.2012, * |
| 银在活性炭上的吸附与表征;刘文宏等;《贵金属》;20040331;第25卷(第1期);第1-6页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102776565A (en) | 2012-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109235024B (en) | Carbon cloth loaded nickel sulfide-molybdenum sulfide heterogeneous nanosheet array structure and preparation method thereof | |
| Wang et al. | All-solid-state Z-scheme Pt/ZnS-ZnO heterostructure sheets for photocatalytic simultaneous evolution of H2 and O2 | |
| CN107946560B (en) | Carbon-limited domain metal or metal oxide composite nano-structure material and preparation method and application thereof | |
| CN108385124B (en) | Preparation method of transition metal/carbon tube/graphene electrocatalyst for hydrogen evolution reaction | |
| CN110272035B (en) | Method for preparing carbon nanocages by catalyzing organic ligands with metal ions, carbon nanocages prepared by method and application of carbon nanocages | |
| CN103268929A (en) | Carbon/copper/metal oxide composite porous material and preparation method and application thereof | |
| CN108588751B (en) | Oxygen-group cobalt-based catalyst, preparation method and application of electrocatalytic oxygen evolution | |
| CN102776565B (en) | Method for preparing nano-structure single crystal silver | |
| CN109473651B (en) | Synthesis of bimetallic sulfide Co by ZIF-67 derivatization8FeS8Method for preparing/N-C polyhedral nano material | |
| Yu et al. | Morphology control and electronic tailoring of CoxAy (A= P, S, Se) electrocatalysts for water splitting | |
| Chen et al. | Preparation of nanostructured Cu 2 SnS 3 photocatalysts by solvothermal method | |
| Fan et al. | Spontaneous growth of CuO nanoflakes and microflowers on copper in alkaline solutions | |
| CN103482674A (en) | Preparation method of copper oxide nanowires and application of copper oxide nanowires in negative electrode of lithium ion battery | |
| CN107597147B (en) | Nano flower-shaped cadmium sulfide @ nickel sulfide thin film heterostructure and preparation method thereof | |
| CN112777634A (en) | Preparation method of bismuth vanadate with high (010) crystal face exposure ratio | |
| Li et al. | Transforming the Charge Transfer Mechanism in the In2O3/CdSe-DETA Nanocomposite from Type-I to S-Scheme to Improve Photocatalytic Activity and Stability During Hydrogen Production | |
| CN102001698B (en) | Preparation method of indium oxide mesoporous nanospheres | |
| Chang et al. | Rapid preparation and photocatalytic properties of octahedral Cu2O@ Cu powders | |
| Xiao et al. | Ultrasonochemical-assisted synthesis of CuO nanorods with high hydrogen storage ability | |
| CN110841680A (en) | Preparation method of nitrogen and sulfur-doped graphene-CuS composite material | |
| CN112144068B (en) | System for synthesizing silicon nanofibers through in-situ electrocatalysis molten salt electrolysis by diaphragm method | |
| CN113512738A (en) | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof | |
| US9567689B2 (en) | Method of growing nanostructured single crystal silver on active carbon | |
| CN102061498B (en) | Preparation method of injector-shaped ZnO nanostructural array for field emission | |
| CN109904410B (en) | Graphene-like carbon-coated nickel selenide composite material and preparation method and application 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150520 Termination date: 20200820 |