CN103014776B - Surface-modified nanosheet-assembled silver microspheres and preparation method thereof - Google Patents
Surface-modified nanosheet-assembled silver microspheres and preparation method thereof Download PDFInfo
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- CN103014776B CN103014776B CN201310009307.3A CN201310009307A CN103014776B CN 103014776 B CN103014776 B CN 103014776B CN 201310009307 A CN201310009307 A CN 201310009307A CN 103014776 B CN103014776 B CN 103014776B
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Abstract
The invention belongs to the technical field of micro material preparation methods, and particularly relates to surface-modified nanosheet-assembled silver microspheres and a preparation method thereof. In a tartaric acid-silver nitrate electrolysis system, an electrochemical deposition method is utilized to prepare the nanosheet-assembled silver microsphere structure under constant voltage, and the nanosheet-assembled silver microsphere structure is effectively subjected to surface modification. The silver microspheres are formed by mutual aggregation of nanosheets with different orientations; and the silver microsphere surface is provided with a surface modification substance in a similar ramiform sheet structure. The silver microspheres prepared by the method are provided with the surface modification substance in a similar ramiform sheet structure, and therefore, have the characteristics of high surface roughness and large specific area. Due to the high surface roughness and large specific area, the silver microspheres in such a structure are hopeful to be used in the fields of Raman enhancement, hydrogen peroxide detection, ultrahydrophobicity, photocatalysis, gas adsorption and the like.
Description
Technical field
The invention belongs to micro materials preparation method technical field, micron ping-pong ball assembled by nanoscale twins of particularly a kind of finishing and preparation method thereof.
Background technology
The micron of argent, nanostructure have unique optics, electricity, magnetics and catalytic performance, can be widely used in biosensor, surface Raman enhancement (SERS) and micromechanical devices etc.And the form of silver-colored micro-nano structure and size will directly affect the performance of its aspect such as optics, magnetics.Such as, nano silver wire is compared with body silver, and light transmission strengthens greatly, and electroconductibility only has small decline; The silver nano-grain of tetrahedron pattern has fabulous plasmon excitation, can increase the light utilization efficiency of photoelectric device.At present, people have prepared controlled silver nanostructured as SERS substrate of different morphologies, such as, and silver nano line array, silver-colored dendrite and flower-shaped silver, micron ping-pong ball etc.Wherein, the micron ping-pong ball be made up of nanoscale twins effectively can improve the sensitivity that SERS detects.If further modification can be done to ping-pong ball surface, increase its surfaceness and specific surface area, then will more be conducive to the raising of detection sensitivity.Meanwhile, the micron ping-pong ball with finishing will be expanded and apply to the fields such as super-hydrophobic, photochemical catalysis, material detection.
Summary of the invention
Not enough for prior art, micron ping-pong ball assembled by nanoscale twins that the invention provides a kind of finishing and preparation method thereof.
A preparation method for the micron ping-pong ball assembled by nanoscale twins of finishing, adopts electrochemical deposition method, with AgNO
3be basic electrolyte system with tartrate, take conductive substrates as negative electrode, graphite is anode, and under constant voltage and magnetic agitation condition, a micron ping-pong ball is prepared in reaction, and concrete steps are as follows:
A. AgNO is configured
3and tartrate mixing solutions is as electrolyte system, wherein AgNO
3and tartaric concentration is 20 g/L ~ 60 g/L, add boron acid for adjusting pH to 2 ~ 5;
B. under 200 r/min ~ 600 r/min magnetic rotor at the uniform velocity stir, take conductive substrates as negative electrode, graphite flake is anode, under 0.5 V ~ 2 V constant voltage, deposit 10 min ~ 180 min;
C. after deposition terminates, deenergization, takes off negative electrode conductive substrates, carefully rinses well with deionized water, dries at 45 DEG C of temperature in clean dry environment, i.e. the obtained micron ping-pong ball assembled by nanoscale twins with finishing.
Described conductive substrates is conductive glass, metal or silicon single crystal.
Described AgNO
3be 1:0.8 ~ 1:1.2 with tartaric mass ratio.
Described AgNO
3and tartrate mixing solutions adopts magnetic stirring apparatus middling speed at the uniform velocity to stir at least 2.5h, makes it mix.
The temperature of described electrochemical deposition is room temperature, or controls its speed of response by reducing temperature.
The micron ping-pong ball assembled by nanoscale twins of finishing, described micron ping-pong ball is that the nanometer silver lamella of different orientation is reunited the micron ping-pong ball formed mutually, and ping-pong ball surface is with the surface modification of dendritic silver lamellar structure.
The diameter of described micron ping-pong ball is 5 μm ~ 12 μm.
Beneficial effect of the present invention is:
The micron ping-pong ball output adopting method of the present invention to prepare is large, be evenly distributed, surfaceness is high and specific surface area is larger.Structurally, it is not only and is reunited the micron ping-pong ball structure formed by nanoscale twins, and all there is the various types of modifier like dendritic lamellar structure on its surface, and these all effectively increase specific surface area and the roughness of micron ping-pong ball.
Accompanying drawing explanation
Fig. 1 is the electromicroscopic photograph of the micron ping-pong ball assembled by nanoscale twins with finishing;
Fig. 2 is the EDS detection figure of this micron of ping-pong ball structure.
Embodiment
Embodiment 1
1. be placed in alcohol respectively after FTO glass acetone being soaked 30 min, each ultrasonic cleaning 10 min in deionized water.
2. weigh 4.0 g AgNO respectively with electronic balance
3, 4.0 g tartrate in the dry beaker of 500ml, then measure 100 ml deionized waters with graduated cylinder and pour in above-mentioned beaker, and are placed in by beaker on magnetic stirring apparatus and stir 3.5 h, make it mix, obtain electrolyte solution.
3. FTO glass is placed in negative electrode, graphite is placed in anode, immerses to fill in the beaker of 100ml electrolyte solution described in the 2nd step, beaker to be placed on magnetic stirring apparatus at the uniform velocity stirred solution, rotating speed is 300 r/min, simultaneously under 1.1 V volts DSs, deposits 70 min.
4. deenergization after arrival setting-up time, careful taking-up FTO glass, repeatedly cleans 3 times ~ 5 times with deionized water, is placed in dry 5 min of air dry oven, be i.e. the obtained micron ping-pong ball assembled by nanometer sheet with finishing.
5. use silicon single crystal and metal substrate instead, repeat above-mentioned technique, the structure be similar to can be obtained.
6. the conductive substrates conductive resin depositing micron ping-pong ball is above sticked on electron microscopic sample platform and prepare SEM test.
As shown in Figure 1: amplified the abundance (150 times) figure can finding out micron ping-pong ball by low power, be evenly distributed; Can find out that ping-pong ball surfaceness is high by upper right corner magnification at high multiple (5000 times) figure, surface is with the modifier of similar dendritic lamellar structure; Lower left corner magnification at high multiple (40000 times) figure provides the dendritic lamellar structure on ping-pong ball surface.
Claims (7)
1. a preparation method for the micron ping-pong ball assembled by nanoscale twins of finishing, is characterized in that: adopt electrochemical deposition method, with AgNO
3be basic electrolyte system with tartrate, take conductive substrates as negative electrode, graphite is anode, and under constant voltage and magnetic agitation condition, a micron ping-pong ball is prepared in reaction, and concrete steps are as follows:
A. AgNO is prepared
3and tartrate mixing solutions is as electrolyte system, wherein AgNO
3and tartaric concentration is 20g/L ~ 60g/L, add boron acid for adjusting pH to 2 ~ 5;
B., under 200r/min ~ 600r/min magnetic rotor at the uniform velocity stirs, take conductive substrates as negative electrode, graphite flake is anode, under 0.5V ~ 2V constant voltage, deposit 10min ~ 180min;
C. after deposition terminates, deenergization, takes off negative electrode conductive substrates, carefully rinses well with deionized water, dries at 45 DEG C of temperature in clean dry environment, i.e. the obtained micron ping-pong ball assembled by nanoscale twins with finishing.
2. method according to claim 1, is characterized in that: described conductive substrates is conductive glass, metal or silicon single crystal.
3. method according to claim 1, is characterized in that: described AgNO
3be 1: 0.8 ~ 1: 1.2 with tartaric mass ratio.
4. method according to claim 1, is characterized in that: described AgNO
3and tartrate mixing solutions adopts magnetic stirring apparatus at the uniform velocity to stir at least 2.5h, makes it mix.
5. method according to claim 1, is characterized in that: the temperature of described electrochemical deposition is room temperature, or controls its speed of response by reducing temperature.
6. the micron ping-pong ball assembled by nanoscale twins of the finishing prepared by the preparation method described in Claims 1 to 5 any one, it is characterized in that: described micron ping-pong ball is that the nanometer silver lamella of different orientation is reunited the micron ping-pong ball formed mutually, and ping-pong ball surface is with the surface modification of dendritic silver lamellar structure.
7. according to claim 6 micron of ping-pong ball, is characterized in that: the diameter of described micron ping-pong ball is 5 μm ~ 12 μm.
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| CN201310009307.3A CN103014776B (en) | 2013-01-09 | 2013-01-09 | Surface-modified nanosheet-assembled silver microspheres and preparation method thereof |
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| CN201310009307.3A CN103014776B (en) | 2013-01-09 | 2013-01-09 | Surface-modified nanosheet-assembled silver microspheres and preparation method thereof |
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| CN103014776B true CN103014776B (en) | 2015-06-10 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361656B (en) * | 2013-06-20 | 2015-06-03 | 北京理工大学 | Method for preparing super-hydrophobicity surface on metallic zinc |
| CN106493387B (en) * | 2016-11-05 | 2018-08-28 | 中国乐凯集团有限公司 | The preparation method of micron ping-pong ball |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182637A (en) * | 2006-11-16 | 2008-05-21 | 方景礼 | Alkalescent chemical silver plating solution |
| CN101323964A (en) * | 2008-07-01 | 2008-12-17 | 南京大学 | Synthetic method of load type floriform silver nanostructured material |
| KR20090092403A (en) * | 2008-02-27 | 2009-09-01 | (주)엘켐텍 | The Micro-Size Hollow Sphere Electrode |
| CN101579746A (en) * | 2008-05-13 | 2009-11-18 | 中国科学院理化技术研究所 | Method for preparing micron-grade superfine silver powder with shape of pinecone, flower or tree |
| CN102233433A (en) * | 2010-05-08 | 2011-11-09 | 中国科学院合肥物质科学研究院 | Micron semisphere composed of silver nano-flakes as well as preparation method and use thereof |
| CN102464295A (en) * | 2010-10-30 | 2012-05-23 | 中国科学院合肥物质科学研究院 | Hollow ball micro/nano structure array with silver nano plates as basic elements and preparation method thereof |
-
2013
- 2013-01-09 CN CN201310009307.3A patent/CN103014776B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182637A (en) * | 2006-11-16 | 2008-05-21 | 方景礼 | Alkalescent chemical silver plating solution |
| KR20090092403A (en) * | 2008-02-27 | 2009-09-01 | (주)엘켐텍 | The Micro-Size Hollow Sphere Electrode |
| CN101579746A (en) * | 2008-05-13 | 2009-11-18 | 中国科学院理化技术研究所 | Method for preparing micron-grade superfine silver powder with shape of pinecone, flower or tree |
| CN101323964A (en) * | 2008-07-01 | 2008-12-17 | 南京大学 | Synthetic method of load type floriform silver nanostructured material |
| CN102233433A (en) * | 2010-05-08 | 2011-11-09 | 中国科学院合肥物质科学研究院 | Micron semisphere composed of silver nano-flakes as well as preparation method and use thereof |
| CN102464295A (en) * | 2010-10-30 | 2012-05-23 | 中国科学院合肥物质科学研究院 | Hollow ball micro/nano structure array with silver nano plates as basic elements and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| Surface characterization of electrodeposited silver on activated carbon for bactericidal purposes;Hector Ortiz-Ibarra et al.;《Journal of Colloid and Interface Science》;ELSEVIER;20070706;第314卷(第2期);第562-571页，参见第563页第2.3节 * |
| 廖学红,朱俊杰,邱晓峰,赵小宁,陈洪渊.类球形和树枝状纳米银的超声电化学制备.《南京大学学报(自然科学)》.2002,第38卷(第1期),第119-第123页. * |
| 王斌,王赪胤.电化学沉积制备纳米银粒子的研究.《德州学院学报》.2009,第25卷(第6期),第31-33页. * |
| 贵金属纳米颗粒的形貌控制合成、自组装与表面增强拉曼散射性质;沈小双;《中国科学技术大学博士学位论文》;20101015;第78-83页 * |
| 银纳米粒子的合成及SERS活性研究;梁红艳;《山东大学硕士学位论文》;20100515;第25-29页 * |
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