CN106757173A - A kind of preparation method of the micro-nano crystal of silver-colored polyhedron without surface ligand - Google Patents
A kind of preparation method of the micro-nano crystal of silver-colored polyhedron without surface ligand Download PDFInfo
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- CN106757173A CN106757173A CN201611056420.7A CN201611056420A CN106757173A CN 106757173 A CN106757173 A CN 106757173A CN 201611056420 A CN201611056420 A CN 201611056420A CN 106757173 A CN106757173 A CN 106757173A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a kind of preparation method of the micro-nano crystal of silver-colored polyhedron without surface ligand, comprise the following steps：S1, the preparation micro-nano crystal of silver-colored polyhedron：To contain Ag+Concentration is that the silver salt solution of 0.01~500mM/L is electrolyte, under conditions of any interval, pH value 0~8 of 1V~0.7Vvs.SHE voltage ranges, the micro-nano crystal of silver-colored polyhedron with height rule structure that electro-deposition is sized to the generation in substrate is carried out；S2, cleaning and drying：After the completion of electro-deposition, substrate is taken out, be vacuum dried after being cleaned using deionized water.The preparation method can make the micro-nano crystal morphology of obtained silver polyhedron, size controllable；Organic ligand molecule need not be added in preparation process, made silver-colored polyhedral surface is without organic ligand；Preparation process is simple, it is easy to operate, Production Time is short, efficiency high, it is adaptable to industrialized production and application.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of micro-nano crystal of silver-colored polyhedron without surface ligand
Preparation method.
Background technology
Colloid chemistry methods synthesis Nano silver grain surface is typically all covered by surface ligand molecule, because synthesis nanometer
Surfactant part, such as cetyl trimethyl bromine ammonium (CTAB), dodecyl are must be added to when example in the solution
Benzene sulfonic acid sodium salt (SDS), polyvinyl pyrrole alkane (PVP) etc. control the formation of nucleus and the growth of nano-particle, prevent nanometer
Particle aggregation.In solution of the nano particle immersion containing another surface ligand with a kind of surface ligand, it is possible to achieve
The displacement sorption of surface ligand.By the displacement of this surface ligand, it is possible to which the ligand molecular for needing is grafted onto a nanometer material
Material surface, realizes the surface modification and functionalization of nano material.But in above-mentioned surface modification process, nano grain surface must
Must be under the protection of certain surface ligand at moment, reunited with preventing directly contact between nano particle, this can give
Some researchs and application bring adverse effect.Such as, in fields such as SERSs (SERS), if mesh to be studied
The effect of mark molecule and nanoparticle surface is weaker than the effect of surface ligand molecule and nanoparticle surface, and target molecule is dense
Degree it is very low when, target molecule would become hard to substitution ligand molecular and occupy surface-active point, this will cause test gained spectrum by because
The presence of ligand molecular and produce many noise signals, while target prickly heat signal is greatly weaker, detection sensitivity is greatly reduced.
Therefore, nano-particle of the synthetic surface without part is carried out in the urgent need to developing a kind of method of high efficiency, low cost.By controlling to deposit
Current potential, electric current, time, concentration of electrolyte and formula and deposition substrate, under without surface ligand, electrodeposition process is successfully used
In control synthesis various metals nano-micro structure, such as iron polyhedron, platinum polyhedron and cuprous oxide polyhedron, but relevant silver polyhedron
The preparation method of structure has not been reported.The present invention is intended to provide a kind of silver-colored polyhedron micro nanocrystalline prepared without surface ligand
Method.The silver-colored polyhedron micro nanocrystalline prepared by the method, not only pattern rule, size are controllable, and solve existing silver
There must be the problem of organic surface active agent part in micro nanocrystalline preparation process, realize " cleaning " silver without surface ligand
Polyhedral preparation.
The content of the invention
Present invention aim to address above mentioned problem, there is provided a kind of silver-colored multiaspect without surface ligand simple to operate, efficient
The preparation method of the micro-nano crystal of body.
In order to solve the above technical problems, the technical scheme is that：A kind of silver-colored polyhedron without surface ligand is micro-nano
The preparation method of crystal, comprises the following steps：
S1, the preparation micro-nano crystal of silver-colored polyhedron：To contain Ag+Concentration is that the silver salt solution of 0.01~500mM/L is electricity
Solution liquid, under conditions of any interval, pH value 0~8 of -1V~0.7Vvs.SHE voltage ranges, carries out electro-deposition in substrate
It is upper to generate the micro-nano crystal of silver-colored polyhedron with height rule structure being sized；
S2, cleaning and drying：After the completion of electro-deposition, substrate is taken out, be vacuum dried after being cleaned using deionized water.
The micro-nano plane of crystal of silver-colored polyhedron for being obtained is adsorbed without any organic ligand.
In above-mentioned technical proposal, linear scan is done using constant voltage method or in the range of setting voltage or in setting voltage model
Enclosing interior use pulse potential technology carries out electro-deposition.Can be by adjusting current potential, potential scanning speed and interval and pulse potential
Amplitude and frequency, realize the regulation and control polyhedron-shaped to silver.
The setting of voltage range, the purpose is to control the speed of Electrodeposited Silver moderate, deposition velocity is too small to be stranded silver-colored nucleation
Difficulty, easily grows particle not of uniform size, when electrodeposition rate is fast, it is impossible to control crystal face to grow, and can grow into irregular structure.
It is that, up to above-mentioned purpose, preferred voltage ranges of the present invention are any interval of -1V~0.7Vvs.SHE voltage ranges.It is all in the present invention
Under the guidance of thought, other voltage ranges chosen in the conventional electrodeposition voltage range of this area fall within protection of the invention
Scope.
According to inventor experimental studies have found that, potential scanning speed difference can cause to grow silver-colored multiaspect of different shapes
Body, the easy growth of cubic body of low potential sweep speed, high potential sweep speed can grow octahedra or irregular structure.It is preferred that
Potential scanning speed is 10mV/s~1V/s, and in the potential scanning speed interval range, silver-colored polyhedral controlled shape exceedes
The interval range, will prepare irregular silver polyhedral structure.Increase pulse potential amplitude and frequency easily grow ten octahedrals
Body or pore space structure, amplitude and frequency hour can deposit silver-colored cube.Preferred pulse potential amplitude is 0~500mV, and frequency is
0~100Hz.It is all under the guidance of inventive concept, selection this area routine potential scanning speed scope or pulse potential amplitude/
Frequency falls within protection scope of the present invention.
In above-mentioned technical proposal, silver-colored polyhedral size is controlled by by sedimentation time.Electrodeposition time can basis
Silver-colored polyhedral size of applied voltage, potential scanning speed, pulse potential amplitude/frequency and final setting confirms.
In the present invention sedimentation time of preferred electro-deposition be 10s~24h, the micro-nano crystalline size of silver-colored polyhedron for being obtained be 10nm~
100μm。
Can also realize adjusting silver-colored polyhedral pattern by inorganic additive in above-mentioned technical proposal, in the electrolyte
Control.The inorganic additive can use but be not limited to contain NH4 +、NO3 -、K+Or Na+In one kind.Electrolyte can with but do not limit
In be addition inorganic electrolyte and various concentrations AgNO3Mixed solution, or silver ammino solution, silver perchlorate solution.Through
Inventor's experimental studies have found that, the introducing of inorganic ions can play the polyhedron-shaped effect of regulation and control silver, such as addition NH4 +、
NO3 -Be conducive to silver-colored octahedral deposition, add K+Or Na+Be conducive to silver-colored cubical deposition.It is preferred that Ag+Concentration be 0.01~
500mM/L, pH value is 0~8, can reach good electrodeposition effect.When pH value is more than 8, Ag+Can precipitate, not during less than 8
Deposited with PH, the silver-colored polyhedron-shaped difference being easily deposited, pore space structure is easily deposited when such as PH is less than 1, PH is left 8
Silver-colored octahedron is easily deposited when right.
In above-mentioned technical proposal, one kind that the material of the substrate can be selected but be not limited in Si, Ti or Au.Based on this
The guidance of invention thought, other substrate materials selected in substrate material commonly used in the art fall within protection model of the invention
Enclose.
What deserves to be explained is, the preparation method of the micro-nano crystal of silver-colored polyhedron without surface ligand that the present invention is provided, its
Innovative point is to control rational electrodeposition condition and concentration of electrolyte, and controlled shape has been synthesized in the case of without surface ligand
Silver-colored polyhedral structure.There is no at present and prepare silver-colored polyhedral precedent using electro-deposition in the case of without surface ligand, thus
The preparation method belongs to pioneer invention creation.Although electrodeposition process is successfully used for control synthesis various metals micro-nano structure,
But the material that can prepare regular polyhedron pattern cans be counted on one's fingers, and reason is to prepare regular texture using electro-deposition techniques at present
The mechanism of micro Nano material also there is no final conclusion, material because the difference of habit may be by the basic nothing of electro-deposition techniques at present
Method makes regular polyhedron structure, and the control method to a certain material structure there is no reference meaning to another material
Justice, is required for groping technical conditions again using electro-deposition techniques to the structure regulating of every kind of new material.The present inventor is through excessive
The experiment of amount hardships obtains the preferred parameter of electrodeposition condition in the present invention, and the preparation method provided using the present invention is not being had
In the case of using organic ligand, while the more than cube of the polyhedral structure prepared, also octahedron, ten octahedrons etc. are very
Many other structures.
The preparation method of the micro-nano crystal of silver-colored polyhedron without surface ligand that the present invention is provided has the advantages that：
1st, the electrodeposition condition of preparation method offer is primarily based on, without any organic surface active agent or other parts
In the case of, the micro-nano crystal of silver-colored polyhedron with height rule structure without surface ligand can be prepared, this is first
The micro-nano crystal of silver-colored polyhedron without surface ligand is obtained by electro-deposition method；
2nd, the preparation method provided by the present invention can make the micro-nano crystal morphology of obtained silver polyhedron, size controllable；
3rd, preparation process is simple, it is easy to operate, Production Time is short, efficiency high, it is adaptable to industrialized production and application.
Brief description of the drawings
Fig. 1 is the three-electrode cell used in embodiment, wherein the structural representation of (A) for three-electrode cell；(B)
It is reference electrode and the structural representation to electrode；
Fig. 2 is the SEM figures of the micro-nano crystal structure of silver-colored polyhedron, wherein (a) is micro- for the silver-colored polyhedron of the preparation of embodiment 1
Nanocrystalline structure；B () is the micro-nano crystal structure of silver-colored polyhedron prepared by embodiment 2；C () is that silver prepared by embodiment 3 is more
The micro-nano crystal structure of face body.
Description of reference numerals：1st, reference electrode；2nd, to electrode；3rd, working electrode.
Specific embodiment
In order to be better understood by the purpose of the present invention and meaning, the present invention is done with reference to the accompanying drawings and detailed description
Further instruction.
As shown in figure 1, in following specific embodiments, using the homemade typical standard three-electrode cell of the present inventor
Electro-deposition operation is carried out, metal platinized platinum is used to electrode, reference electrode is using the Ag/AgCl being sealed in saturation KCl solution.Need
It is noted that using which kind of electrolytic cell, and which kind of material is used to electrode, reference electrode, it is not limited to following specific realities
Apply example.
Embodiment 1
S1, the preparation micro-nano crystal of silver-colored polyhedron：Electrolyte is addition K+、Na+It is 10mM AgNO with concentration3Solution,
PH value is 4, voltage range be -1V~0.5Vvs.SHE, with Si as substrate, using potentiostatic method in substrate electro-deposition 20s；
S2, cleaning and drying：Substrate is taken out from electrolyte, after being cleaned using deionized water, is put into vacuum drying chamber
Dry, obtain the micro-nano crystal of silver-colored polyhedron without surface ligand.
The micro-nano crystal of silver-colored polyhedron without surface ligand is obtained for cube, size is 20nm~1 μm, such as Fig. 2 institutes
Show, wherein (a) is the silver-colored micro-nano crystal structure of polyhedron manufactured in the present embodiment.
Embodiment 2
S1, the preparation micro-nano crystal of silver-colored polyhedron：Electrolyte is addition K+、Na+It is 200mM AgNO with concentration3Solution,
PH value is 7, and voltage range is -0.7V~0.2Vvs.SHE, with Ag as substrate, is scanned using Linear Circulation, sweep speed 10mV/
S carries out electro-deposition 20h in substrate；
S2, cleaning and drying：Substrate is taken out from electrolyte, after being cleaned using deionized water, is put into vacuum drying chamber
Dry, obtain the micro-nano crystal of silver-colored polyhedron without surface ligand.
The micro-nano crystal of silver-colored polyhedron without surface ligand is obtained to cut top cube or cuboctahedron, size is 10
μm~90 μm, as shown in Fig. 2 wherein (b) is the silver-colored micro-nano crystal structure of polyhedron manufactured in the present embodiment.
Embodiment 3
S1, the preparation micro-nano crystal of silver-colored polyhedron：Electrolyte is that concentration is 50mM silver ammonium salt solutions, and pH value is 1, voltage range
It is -0.1V~0.6Vvs.SHE, with Au as substrate, using pulse potential technology, pulse potential amplitude is 20mV, and frequency is
50Hz, carries out electro-deposition 5h in substrate；
S2, cleaning and drying：Substrate is taken out from electrolyte, after being cleaned using deionized water, is put into vacuum drying chamber
Dry, obtain the micro-nano crystal of silver-colored polyhedron without surface ligand.
It is octahedron to obtain the micro-nano crystal of silver-colored polyhedron without surface ligand, and size is 50nm~40 μm, such as Fig. 2 institutes
Show, wherein (c) is the silver-colored micro-nano crystal structure of polyhedron manufactured in the present embodiment.
One of ordinary skill in the art will be appreciated that embodiment described here is to aid in reader and understands this hair
Bright principle, it should be understood that protection scope of the present invention is not limited to such especially statement and embodiment.This area
Those of ordinary skill can according to these technical inspirations disclosed by the invention make it is various do not depart from essence of the invention other are each
Plant specific deformation and combine, these deformations and combination are still within the scope of the present invention.
Claims (7)
1. a kind of preparation method of the micro-nano crystal of silver-colored polyhedron without surface ligand, it is characterised in that：Comprise the following steps：
S1, the preparation micro-nano crystal of silver-colored polyhedron：To include Ag+Concentration is that the silver salt solution of 0.01~500mM is electrolyte,
Under conditions of any interval, pH value 0~8 of -1V~0.7Vvs.SHE voltage ranges, carry out electro-deposition and generated in substrate
The micro-nano crystal of silver-colored polyhedron with height rule structure being sized；
S2, cleaning and drying：After the completion of electro-deposition, substrate is taken out, be vacuum dried after being cleaned using deionized water.
2. the preparation method without surface ligand silver polyhedron micro-nano crystal according to claim 1, it is characterised in that：Institute
The micro-nano plane of crystal of silver-colored polyhedron of acquisition is adsorbed without any organic ligand.
3. the preparation method without surface ligand silver polyhedron micro-nano crystal according to claim 1, it is characterised in that：Adopt
Linear scan is made of constant voltage method or in the range of setting voltage or is carried out using pulse potential technology in the range of setting voltage
Electro-deposition.
4. the preparation method without surface ligand silver polyhedron micro-nano crystal according to claim 3, it is characterised in that：Institute
State and done in the range of setting voltage linear scan and carry out electro-deposition, potential scanning speed is 10mV/s~1V/s.
5. the preparation method without surface ligand silver polyhedron micro-nano crystal according to claim 3, it is characterised in that：Institute
State carries out electro-deposition in the range of setting voltage using pulse technique, and pulse potential amplitude is 0~500mV, and frequency is 0~
100Hz。
6. according to any described preparation methods without the surface ligand silver micro-nano crystal of polyhedron of claim 1-5, its feature
It is：The sedimentation time of electro-deposition is 10s~24h.
7. according to any described preparation methods without the surface ligand silver micro-nano crystal of polyhedron of claim 1-5, its feature
It is：The micro-nano crystalline size of silver-colored polyhedron is 10nm~100 μm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337847A (en) * | 2021-05-11 | 2021-09-03 | 武汉大学 | Preparation method of cubic copper particles with multi-edge structure |
| CN113579563A (en) * | 2021-07-28 | 2021-11-02 | 电子科技大学 | Nano cubic silver solder paste, interconnection structure and welding method |
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| CN105386119A (en) * | 2015-10-30 | 2016-03-09 | 西北师范大学 | Preparation method of dendritic silver nanocrystalline coating using electrodeposition |
| CN105908220A (en) * | 2016-05-06 | 2016-08-31 | 上海应用技术学院 | Method for manufacturing micro-nano-silver dendritic crystal through liquid-phase electrodeposition |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040232386A1 (en) * | 2001-08-22 | 2004-11-25 | Jun Yorita | Conductive paste and conductive film musing it, plating method and production method for fine metal component |
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| CN102212847A (en) * | 2011-05-04 | 2011-10-12 | 湖南科技大学 | Method for preparing nanometer silver granules |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337847A (en) * | 2021-05-11 | 2021-09-03 | 武汉大学 | Preparation method of cubic copper particles with multi-edge structure |
| CN113337847B (en) * | 2021-05-11 | 2022-03-04 | 武汉大学 | Preparation method of cubic copper particles with multi-edge structure |
| CN113579563A (en) * | 2021-07-28 | 2021-11-02 | 电子科技大学 | Nano cubic silver solder paste, interconnection structure and welding method |
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